WO2022065520A1 - Co-modified organopolysiloxane and use thereof - Google Patents
Co-modified organopolysiloxane and use thereof Download PDFInfo
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- WO2022065520A1 WO2022065520A1 PCT/JP2021/037003 JP2021037003W WO2022065520A1 WO 2022065520 A1 WO2022065520 A1 WO 2022065520A1 JP 2021037003 W JP2021037003 W JP 2021037003W WO 2022065520 A1 WO2022065520 A1 WO 2022065520A1
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 128
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 125000005353 silylalkyl group Chemical group 0.000 claims abstract description 22
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 20
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- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- A61K8/29—Titanium; Compounds thereof
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Definitions
- the present invention has a specific hydrocarbon group such as a specific silicon-containing organic group, a hydrophilic group and a long-chain alkyl group in the molecule in a specific ratio, and has a constant HLB value and viscosity.
- the present invention relates to a co-modified organopolysiloxane having excellent affinity with various oil agents and having high usefulness as a powder treatment agent, and its use.
- the co-modified organopolysiloxane specifically disclosed in Patent Document 7 realizes a higher powder dispersion performance than the conventional siloxane component, but it can be used as an oil agent in a part of the low HLB region.
- the powder dispersion of No. 1 When the powder dispersion of No. 1 is formed, thickening and decrease in fluidity over time may occur, leaving room for improvement in its stability over time.
- powder dispersions that have a high affinity for a wider variety of oils and have excellent stability over time.
- Formable co-modified organopolysiloxanes are sought after in the market.
- Patent No. 2719303 Japanese Unexamined Patent Publication No. 10-167946 Japanese Unexamined Patent Publication No. 2002-38013 International Publication Patent WO2011 / 049246 Gazette International Publication Patent WO2011 / 049248 Gazette International Patent Publication No. WO2011 / 136394 Japanese Unexamined Patent Publication No. 2013-151657 (Patent No. 63698887)
- the present invention has been made to solve the above problems, and has excellent affinity and compatibility with a wide range of cosmetic raw materials (particularly different types of oils), and when used in combination with powder, it causes thickening and poor dispersion. It is an object of the present invention to provide a co-modified organopolysiloxane that is difficult to cause and can form a good and stable slurry. Further, the present invention comprises a powder treatment agent containing the organopolysiloxane, a powder surface-treated with the powder treatment agent, and a powder composition containing the co-modified organopolysiloxane copolymer. Furthermore, it is an object of the present invention to provide a powder dispersion in oil containing an oil agent, and an external preparation composition containing these, particularly a make-up cosmetic and a method for producing the same.
- the present inventors have an HLB in the range of 0.5 to 2.0, a viscosity at 25 ° C. in the range of 200 to 1500 mPa ⁇ s, and a specific hydrophilic group in the molecule.
- Q C6 to 30 long-chain hydrocarbon groups (R2), and organic silicon-containing organic groups (L1) selected from groups having a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure are specified.
- the co-modified organopolysiloxane according to the present invention has excellent affinity and compatibility not only with silicone oil but also with non-silicone organic oils (for example, hydrocarbon oil and fatty acid ester oil). It can be particularly preferably used for external preparation compositions such as cosmetics containing powders and in combination with different kinds of oils.
- non-silicone organic oils for example, hydrocarbon oil and fatty acid ester oil.
- a modified organopolysiloxane can be provided.
- a powder treatment agent containing the organopolysiloxane, a powder surface-treated with the powder treatment agent, and a powder composition containing the co-modified organopolysiloxane copolymer is provided.
- a powder dispersion in oil containing an oil agent and an external preparation composition containing these, particularly a make-up cosmetic, and a method for producing the same are provided.
- the co-modified organopolysiloxane of the present invention its use as various treatment agents (surfactants or surface treatment agents), particularly its use as a powder treatment agent and its use as a cosmetic raw material will be described in detail. Further, a powder dispersion in oil using the co-modified organopolysiloxane of the present invention, an external preparation, preferably a cosmetic, and particularly preferably a make-up cosmetic will be described in detail.
- the co-modified organopolysiloxane of the present invention is the same as the co-modified organopolysiloxane described in Patent Document 5 (International Publication Patent WO2011 / 049248A) and Patent Document 7 (Japanese Patent Laid-Open No.
- the co-modified organopolysiloxane according to the present invention is a chain polysiloxane having a trimethylsiloxy terminal represented by the structural formula (1) described later, and a silylalkyl group having a carbosiloxydendron structure at the side chain site thereof.
- an organic silicon-containing organic group (L1) selected from groups having a siloxane macromonomer structure, a specific hydrophilic group (Q), and a long-chain hydrocarbon group (R2) having 6 to 30 carbon atoms in a specific ratio.
- the HLB is in the range of 0.5 to 2.0
- the viscosity at 25 ° C. is in the range of 200 to 1500 mPa ⁇ s.
- the value of the hydrophilic lipophilic balance is a value defined by "(total molecular weight of hydrophilic group portion / total molecular weight) x 20", and is in the co-modified organopolysiloxane of the present invention. Therefore, the value needs to be in the range of 0.5 to 2.0, and may be in the range of 1.1 to 2.0, particularly from the viewpoint of performance as a powder dispersant. It is particularly preferably in the range of .5 to 2.0.
- the values of a to d particularly the value of c that affects the number of bonds of the hydrophilic group (Q), need to be a value in which the HLB value of the entire molecule satisfies the above range. be.
- the HLB value is outside the above range, particularly when the HLB value is less than the lower limit and the content of the hydrophilic group (Q) in the molecule is small, the co-modified organopolysiloxane represented by the structural formula (1). Even so, the solid surface cannot be sufficiently coated, and the slurry tends to thicken over time, and the performance as a powder treatment agent may be insufficient.
- the hydrophilic group (Q) according to the present invention preferably a diglycerin derivative group-containing organic group or sugar alcohol.
- the co-modified organopolysiloxane according to the present invention needs to have a viscosity at 25 ° C. in the range of 200 to 1500 mPa ⁇ s from the viewpoint of handling workability as a powder treatment agent, and in particular.
- the viscosity is preferably in the range of 300 to 1450 mPa ⁇ s, and particularly preferably in the range of 700 to 1450 mPa ⁇ s. preferable.
- the co-modified organopolysiloxane has the above-mentioned HLB and has a specific hydrophilic group, an organic silicon-containing organic group, and a monovalent hydrocarbon group having 6 to 30 carbon atoms, its viscosity is high. If the upper limit is exceeded, the handling workability as a powder treatment agent deteriorates, and in particular, when preparing a powder dispersion using a non-silicone-based organic oil agent (for example, a hydrocarbon oil and a fatty acid ester oil). In addition to insufficient work efficiency and dispersibility, the obtained powder dispersion (particularly, the slurry which is a powder dispersion in oil) thickens over time, and the dispersion of the powder is insufficient. This makes it difficult to use as a raw material for cosmetics, and depending on the conditions, it may not be possible to prepare a powder dispersion at all.
- a non-silicone-based organic oil agent for example, a hydrocarbon oil and a fatty acid este
- the viscosity of the co-modified organopolysiloxane is greatly affected by the type and content of the hydrophilic group (Q) and the degree of polymerization n1 to n4 of each diorganosiloxy unit in the general formula (1) and the sum thereof (n1 + n2 + n3 + n4). Therefore, the values of n1 to n4 in the structural formula (1) need to be numbers that satisfy the above viscosity range, and particularly preferably, the range of (n1 + n2 + n3 + n4) is 8 to 25, and n1 is 3. It is particularly preferable that n2 is 1 to 10, n3 is 0.1 to 10, and n4 is 0.5 to 2.0.
- the covariant organopolysiloxane according to the present invention has the following structural formula (1): (1) It is represented by.
- R 1 is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms, and does not contain other groups corresponding to R 2 , L 1 , and Q, and is industrially used. Is preferably a methyl group or a phenyl group.
- R2 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, and in particular, with a non-silicone oil such as a hydrocarbon oil (cosmetic raw material). Affinity can be improved.
- R 2 is an alkyl group having 6 to 30 carbon atoms, and examples thereof include a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, undecyl, and a hexadecyl group, and in particular, the number of carbon atoms is 8. Up to 20 alkyl groups are preferred.
- L 1 is an organosilicon-containing organic group selected from a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure, and specifically, L 1 is an organosilicon-containing organic group.
- the following general formula (2) when i 1: (2) (In the formula, R 1 is the same group as described above, RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, Z is a divalent organic group, and i is a silyl represented by Li.
- the layer of the alkyl group indicates the layer of the alkyl group, and when the number of layers which is the number of repetitions of the silylalkyl group is c, it is an integer of 1 to c, the number of layers c is an integer of 1 to 10, and Li + 1 is i less than c.
- Ai is a number in the range of 0 to 3
- a silylalkyl group having a siloxane dendron structure The following general formula (2'): (2') (In the formula, R 11 is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group.
- T is a number in the range of 2 to 10
- r is a number in the range of 1 to 500
- (2') In the formula, R 11 and r are as described above), which is one or more groups selected from the chain-like organosiloxane groups.
- the groups represented by L 1 may be the same or different.
- a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure may be contained in the same molecule, and the silylalkyl group has an organic silicon-containing organic group having a different degree of branching (generation).
- the group having a siloxane macromonomer structure it may be a combination of organic silicon-containing organic groups having different degrees of polymerization.
- RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, and industrially, it is preferably a methyl group or a phenyl group.
- the number of layers c is preferably an integer of 1 to 3, and more preferably 1 or 2.
- the group represented by L1 is represented as follows.
- R2 and Z are the same groups as described above.
- ai is a number in the range of 0 to 3 independently, and in the structure represented by the formulas (2-1) to (2-3) when the number of layers is 1 to 3, a1 and a1 a2 and a3 are independently numbers in the range 0-3. These ai are particularly preferably in the range of 0 to 1, and particularly preferably 0.
- Z is an independently divalent organic group, and specifically, a functional group having a silicon-bonded hydrogen atom and an unsaturated hydrocarbon group such as an alkenyl group, an acryloxy group, or a methacrylate group at the end.
- a functional group having a silicon-bonded hydrogen atom and an unsaturated hydrocarbon group such as an alkenyl group, an acryloxy group, or a methacrylate group at the end.
- Examples thereof include a divalent organic group formed by the addition reaction of the above, and the group is not limited to these functional groups and can be appropriately selected depending on the method for introducing a silylalkyl group having a carbosiloxane dendrimer structure.
- Z in the present invention is preferably an alkylene group having 2 to 10 carbon atoms, and most preferably an ethylene group.
- the group represented by L 1 may be a siloxane macromonomer structure-containing group bonded to a silicon atom constituting the main chain via an oxygen or an alkylene group, is hydrophobic, and exhibits a certain water repellency / oil resistance. It is a functional group, and an excellent surfactant and powder treatment agent can be provided to the organopolysiloxane copolymer according to the present application without impairing the feel derived from the hydrophilic functional group.
- the group represented by L 1 may be a functional group represented by the above general formula (2') and general formula (2'').
- R 11 is industrially particularly preferably a long-chain alkyl group in which a methyl group, a phenyl group or a hydroxyl group is raised, a part of R 11 is a methyl group, and a part is a long-chain alkyl group having 8 to 30 carbon atoms.
- at least one of R 11 is a monovalent hydrocarbon group such as a methyl group
- t is a number in the range of 2 to 10
- r is in the range of 1 to 500. It is a number, and from the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and particularly preferably a number in the range of 2 to 30.
- the hydrophilic group Q is a portion that imparts hydrophilicity to the covariant organopolysiloxane according to the present application, and is generally a functional group derived from a hydrophilic compound.
- Q defined as described above has monohydric or higher alcohols, polyether compounds, (poly) glycerin compounds, and (poly) glycidyl ethers whose molecular chain ends may be partially blocked by hydrocarbons.
- a functional group derived from a system compound or a hydrophilic saccharide can be preferably exemplified.
- Q is a polyhydric alcohol-containing organic group in the above structural formula (1) and the like from the viewpoint of the characteristics as a powder treatment agent, particularly the dispersion characteristics of inorganic powder. It is preferably present, and particularly preferably a (poly) glycerin residue or a sugar alcohol residue. From the viewpoint of suppressing the overall viscosity of the co-modified organopolysiloxane, Q is a hydrophilic group derived from a (poly) glycerin-based compound, and is derived from (poly) glycerin. Most preferably, it is a hydrophilic group.
- it is a (poly) glycerin monoallyl ether, (poly) glyceryl eugenol, and is a hydrophilic group derived from a (poly) glycerin-based compound having a monoglycerin, diglycerin, triglycerin or tetraglycerin structure. Is preferable, and a hydrophilic group which is a diglycerin derivative is most suitable.
- the diglycerin derivative group has the following structural formula (5): -R 5 -OX m -H (5) It is a diglycerin derivative group represented by.
- R5 is a divalent organic group containing no oxyalkylene structure having an average value of 2 or more repetitions of the oxyalkylene unit, and is preferably an alkylene group having 2 to 10 carbon atoms.
- the average value of the number of repetitions for each glycerin unit is in the range of 1.1 to 2.9, preferably the average value of the number of repetitions is in the range of 1.5 to 2.4, and more preferably. It ranges from 1.8 to 2.2, most preferably an average of 2. That is, the glycerin derivative group which is Q mainly contains a diglycerin derivative group.
- the diglycerin derivative group preferably has a structure in which the repeating structure of the glycerin unit does not have a branch, but a part thereof has a branched structure such as a polyglycerol group or a polyglycidyl ether group. May be.
- the diglycerin derivative group-containing organic group has the following general formula (5-1).
- (5-1) (In the formula, R 5 represents a divalent organic group having no oxyalkylene structure in which the average value of the number of repetitions of the oxyalkylene unit is 2 or more), or the following general formula (5-2).
- (5-2) ( In the formula, R5 is as described above) is a diglycerin derivative group-containing organic group.
- the diglycerin derivative group-containing organic group is preferably a hydrophilic group derived from diglycerin monoallyl ether or diglyceryl eugenol.
- the sugar alcohol-containing organic group in this case corresponds to the structural formula (3-1) or (3-2), and the structural formula: -C 3 H 6 -OCH 2 [CH (OH)] 3 CH 2 OH, Alternatively, it is a xylitol residue represented by the structural formula: -C 3 H 6 -OCH ⁇ CH (OH) CH 2 OH ⁇ 2 .
- n1 to n4 representing the average degree of polymerization of each diorganosiloxy unit
- (n1 + n2 + n3 + n4) is a number in the range of 2 to 50, preferably 5 to 40, and particularly preferably. It is 8 to 25.
- n1 is a number in the range of 0 to 20, more preferably 3 to 10.
- n2 is a number in the range of 1-10, more preferably 1.0-5.0.
- n3 is a number in the range of 0.1 to 10, and more preferably 0.1 to 5.
- n4 is a number in the range of 0.3 to 2.5, more preferably 0.5 to 2.0.
- n4 affects the content of the hydrophilic group Q, n4 is in the range where the HLB value of the entire molecule is 0.5 to 2.0, and more preferably 1.5 to 2.0. Especially preferred is the number of ranges.
- the co-modified organopolysiloxane according to the present invention is an organic silicon-containing organic having one carbon-carbon double bond at one end of the molecular chain with respect to the organopolysiloxane having a reactive functional group such as Si—H.
- a compound having a group for example, the above-mentioned silylalkyl group
- a hydrophilic compound having a reactive functional group such as an alkenyl group (for example, diglycerin monoallyl ether, etc.), and a carbon-carbon double bond at one end of the molecular chain. It can be obtained by carrying out an addition reaction with an unsaturated long-chain hydrocarbon compound having.
- the reaction it is preferable to add the above-mentioned raw materials to an organopolysiloxane having a reactive functional group such as Si—H in multiple steps, and hydrosilylation is performed from the viewpoint of reaction control, purity and yield. It is preferable to carry out an addition reaction in the presence of a reaction catalyst. Further, the crude product of the co-modified organopolysiloxane obtained by the addition reaction may be purified by deodorizing treatment by hydrogenation reaction in the presence of a hydrogenation catalyst in a solvent or no solvent, and may be purified by an acidic substance. A low odor treatment may be performed. Further, the co-modified organopolysiloxane according to the present invention may be obtained as a mixture with a hydrophilic compound having a reactive functional group such as an alkenyl group.
- the reaction, purification, and low odor due to the acidic substance disclosed by the applicants in paragraphs 0110 to 0122 of Patent Document 5 International Publication Patent WO2011 / 049248. It is possible to adopt a method common to the conversion process and the like.
- the co-modified organopolysiloxane can be substantially deodorized, it is solid at 25 ° C., water-soluble, and is an aqueous solution at 25 ° C. when 50 g is dissolved in 1 L of ion-exchanged water.
- acidic inorganic salts preferably sodium hydrogensulfate or the like
- a reaction system for example, a reaction vessel such as a flask
- a co-modified organopolysiloxane composition synthesized by a hydrosilylation reaction and stirred.
- treatment (2) Hydrolysis treatment in which acidic inorganic salt and water or acidic inorganic salt and water and a hydrophilic solvent are added and stirred.
- the treatment step with the acidic inorganic salt is preferably carried out in the presence of water and / or a hydrophilic medium.
- a stripping step for removing a low boiling point (propionaldehyde, etc.) which is a causative substance of odor it is preferable to include a stripping step for removing a low boiling point (propionaldehyde, etc.) which is a causative substance of odor, and the treatment with the above-mentioned acidic substance and stripping of the causative substance of odor are carried out. , It is preferable to perform it multiple times.
- an amount of an alkaline buffer (sodium phosphate, potassium phosphate, etc.) corresponding to 100 ppm to 50,000 ppm is further added. It is preferable to neutralize by adding sodium citrate, sodium acetate, sodium hydrogen carbonate, etc. from the viewpoint of low odor.
- filtration may be performed by a known method.
- the novel co-modified organopolysiloxane (hereinafter, also referred to as “component (A)”) according to the present invention is hydrophobic and has a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group having the same molecule. Since it has a low viscosity and generally has a low HLB, it is excellent in handleability, work efficiency, lipophilic raw material and compounding stability, and is therefore useful as various treatment agents and cosmetic raw material components. It is extremely useful as a surfactant or surface treatment agent used in a material, particularly as a powder treatment agent or powder dispersant used for surface treatment of powder or dispersion of powder.
- the co-modified organopolysiloxane according to the present invention has low viscosity and low HLB, and can be oriented on the surface of various powders to impart appropriate water repellency. Therefore, it is intended for surface treatment and dispersion of cosmetic powders. , Can be suitably used as a powder surface treatment agent.
- the co-modified organopolysiloxane according to the present invention has higher dispersion stability in mixed oil-based, especially non-silicone-based organic oil agents, when used as a powder treatment agent, as compared with known co-modified organopolysiloxanes.
- the conventional powder is used. Even for powders that were difficult to stably disperse with a treatment agent, it is characterized by providing a powder dispersion in oil having excellent stability, which is less likely to cause aggregation, sedimentation, and thickening over time.
- novel co-modified organopolysiloxane according to the present invention can also be used as a feel improver, a moisturizer, a binder, and an adhesive / adhesive for the skin (Skin Adhesive). It can also be used as a film agent and a viscosity adjuster by combining with water.
- the co-modified organopolysiloxane of the present invention has good compatibility with various other hydrophilic and hydrophobic components in cosmetics, and improves the dispersibility and stability of the powder in cosmetics containing powder. can do. Therefore, the powder treatment agent of the present invention and the powder surface treatment agent of the present invention can improve the stability of the cosmetic containing the powder and the uniform dispersibility of the powder.
- the cosmetic containing the powder surface-treated with the powder surface treatment agent is characterized by high stability and the powder being uniformly dispersed in the cosmetic.
- the blending amount of the co-modified organopolysiloxane in the powder treatment agent of the present invention is not particularly limited as long as the powder treatment effect is exhibited, but is, for example, 50 to 100% by weight (mass)%. 70 to 100% by mass is preferable, and 90 to 100% by mass is more preferable.
- the blending amount of the co-modified organopolysiloxane and the powder or the colorant is 0 with respect to 100 parts by mass of the powder or the colorant. .1 to 30 parts by mass is preferable, and the range of 0.5 to 10 parts by mass is particularly preferable. If it is less than the lower limit, the effect of the surface treatment may not be sufficient, and if the treatment amount exceeds the upper limit, no further significant change in texture occurs, and the powder and the covariant organopolysiloxane tend to be a uniform mixture. Increase.
- the co-modified organopolysiloxane according to the present invention can be used for treating the powder surface by using a known method. These methods are not particularly limited, but can be appropriately selected from the following methods, for example. 1. 1. A method of surface-treating a target powder by dispersing it in a medium selected from an organic solvent containing a treatment agent. 2. 2. A method in which powder and a powder treatment agent are mixed and then surface-treated using a crusher such as a ball mill or jet mill. 3. 3. A treatment method in which a treatment agent is mixed with a solvent, powder is dispersed and adsorbed on the surface, and then dried and sintered.
- the present invention also relates to a powder composition containing (A) a co-modified organopolysiloxane according to the present invention and (B) a powder or a colorant.
- the powder composition can be obtained by mixing (B) a powder or a colorant with (A) the co-modified organopolysiloxane according to the present invention by the above method or the like, and the surface treatment of the powder and the powder can be obtained. Regardless of the purpose, such as improving the dispersibility of the body and premixing for cosmetic ingredients.
- the powder dispersion in oil referred to in the present invention is a powder composition obtained as described above dispersed in an oil agent, or a co-modified organopolysiloxane dissolved or dispersed in the oil agent. It means a product in which powder is added and mixed and dispersed, and the form thereof is a liquid dispersion. Such a liquid dispersion may be referred to as a "slurry".
- the co-modified organopolysiloxane according to the present invention may be an inorganic powder such as zinc oxide that cannot be sufficiently treated under the same conditions as the co-modified organopolysiloxane disclosed in Patent Document 5 above. It is useful in that a low-viscosity slurry can be prepared.
- the above-mentioned oil agent is not particularly limited as long as a liquid dispersion can be prepared, and is generally used as a component of cosmetics. It is usually liquid at room temperature, but is a solid such as wax. It may be in the form of a highly viscous and viscous gum or paste, which will be described later.
- an oil agent one or more oil agents selected from (C) silicone oil, which is liquid at 5 to 100 ° C., a non-polar organic compound, or a low-polar organic compound, are suitable.
- an oil containing one or more selected from (C1) silicone oil which is liquid at 5 to 100 ° C. and (C2) hydrocarbon oil and fatty acid ester oil are suitable.
- the dispersion in oil of the present invention can be appropriately prepared by a known method such as the following method. 1. 1. A method of adding and dispersing the powder composition obtained as described above in an oil agent such as ester oil or silicone oil. 2. 2. A method in which a covariant organopolysiloxane is dissolved or dispersed in the above oil, powder is added thereto, and the mixture is mixed with a dispersion device such as a ball mill, a bead mill, or a sand mill. Then, the obtained powder dispersion in oil can be directly blended into the external preparation composition (particularly, cosmetics).
- an oil agent such as ester oil or silicone oil.
- the powder composition and the dispersion in oil containing the co-modified organopolysiloxane according to the present invention can be suitably used as an external preparation composition, particularly as a cosmetic or a cosmetic raw material.
- the (B) powder or colorant used in the powder composition and the powder dispersion in oil according to the present invention is generally used as a component of cosmetics, and is a white and colored pigment, and a constitution. Contains pigments. White and colored pigments are used for coloring cosmetics and the like, while extender pigments are used for improving the feel of cosmetics and the like. As the "powder" in the present invention, white and colored pigments usually used in cosmetics and extender pigments can be used without particular limitation. In the present invention, it is preferable to mix one kind or two or more kinds of powders.
- Powder shape (spherical, rod-shaped, needle-shaped, plate-shaped, indefinite shape, spindle-shaped, cocoon-shaped, etc.), particle size (fumes, fine particles, pigment grade, etc.), and particle structure (porous, non-porous, etc.) Etc.) is not limited in any way, but it is preferable that the average primary particle size is in the range of 1 nm to 100 ⁇ m.
- these powders or colorants are blended as pigments, one or more selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle size in the range of 1 nm to 20 ⁇ m. Is preferably blended.
- the powder examples include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment and the like, and a composite of these is used. be able to. Further, those having a water-repellent treatment on these surfaces can be mentioned.
- an inorganic powder having an ultraviolet absorbing / scattering ability such as titanium oxide, zinc oxide, iron oxide, cerium oxide and a composite thereof is preferable, and the surface thereof is particularly treated with a water repellent treatment.
- the one that has been done is particularly preferable.
- the composite refers to a surface-treated powder, a powder in which other inorganic particles are dispersed inside the inorganic powder, and the like.
- the mixture of (A) the co-modified organopolysiloxane and (B) the powder or the colorant has a form in which the powder is dispersed in the co-modified organopolysiloxane, and the blending amount of the powder in the mixture is particularly limited. Although not, the range of 50 to 99% by mass of the whole mixture is preferable, and 80 to 90% by mass is more preferable.
- the oil agent used for the powder dispersion in oil according to the present invention is preferably one or more selected from (C) silicone oil, non-polar organic compound or low-polar organic compound which is liquid at 5 to 100 ° C.
- the non-polar organic compound and the low-polar organic compound are preferably hydrocarbon oil and fatty acid ester oil.
- the co-modified organopolysiloxane according to the present invention is an oil agent containing not only (C1) a silicone oil liquid at 5 to 100 ° C. but also (C2) one or more selected from hydrocarbon oils and fatty acid ester oils. Since it has an excellent affinity for the oil and can form a stable powder dispersion (slurry, etc.) in oil, it is a mixed oil agent of an oil agent as a component (C1) and an oil agent as a component (C2), or these. It is extremely useful as a cosmetic raw material and an external preparation composition containing both of them.
- the oil agent one kind or two or more kinds selected from known vegetable fats and oils, animal fats and oils, higher alcohols, liquid fatty acid triglyceride, artificial sebum, and fluorine-based oil may be used in combination. Since the co-modified organopolysiloxane exhibits excellent dispersibility even with respect to these non-silicone oils, hydrocarbon oils and fatty acid ester oils can be stably blended into cosmetics, and the moisturizing properties of these non-silicone oils. Can be maintained. Therefore, the covariant organopolysiloxane can improve the stability of these non-silicone oils over time in cosmetics.
- hydrocarbon oil and / or fatty acid ester oil in addition to the refreshing feel peculiar to silicone oil, it retains moisture on the skin and moisturizes the skin and hair with cosmetics. It has the advantages of being able to impart a moisturizing feeling (also referred to as "moist feeling") and a smooth feeling, and not impairing the stability of the cosmetics over time. Further, for cosmetics containing hydrocarbon oil and / or fatty acid ester oil and silicone oil, these moisturizing components (hydrogen hydrocarbon oil and / or fatty acid ester oil) are applied on the skin or hair in a more stable and uniform state. Therefore, the moisturizing effect of the moisturizing ingredient on the skin is improved.
- a cosmetic containing a silicone oil together with a non-silicone oil may give a smoother and moist feel than a cosmetic containing only a non-silicone oil (hydrocarbon oil, fatty acid ester oil, etc.). There is an advantage that it can be done.
- fluorine-based oil examples include perfluoropolyether, perfluorodecalin, and perfluorooctane.
- the blending amount of the oil agent in the powder dispersion in oil of the present invention is not particularly limited, but it is preferably blended in the range of 0.1 to 50% by mass in the raw material for cosmetics, and 0. 5 to 25% by mass is more preferable.
- the co-modified organopolysiloxane, a powder composition containing the same, or a powder dispersion in oil can be suitably used as an external preparation composition, particularly as a cosmetic or a raw material for cosmetics, and these External preparation compositions, particularly cosmetic or pharmaceutical external preparation compositions, are included in the present invention.
- the co-modified organopolysiloxane, a powder composition containing the same, or a powder dispersion in oil is suitable as a raw material for make-up cosmetics, and an external preparation composition (makeup) containing these is suitable.
- an external preparation composition makeup
- the cosmetics of the present invention further include (D) water, alcohols such as ethanol (including use as a premix), (E) other surfactants, (F) polyhydric alcohols and / or lower monovalents. Alcohol, (G) inorganic salts and / or organic acid salts, (H) crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax , Alkyl-modified silicone resin wax, Silicone polyether elastomer gel, PITUITOUS SILICONE FLUIDS, Liquid and micro-crosslinkable organopolysiloxane, etc.
- alcohols such as ethanol (including use as a premix)
- E other surfactants
- F polyhydric alcohols and / or lower monovalents.
- Alcohol inorganic salts and / or organic acid
- Silicone components other than (A), (J) Water-soluble polymer, (K) UV protection Ingredients (including a combination of an inorganic and organic UV protection component / UV-A compatible UV protection component and a UV-B compatible UV protection component) can be blended, and these can be blended with the above patents. It is the same as that disclosed in paragraphs 0101 to 0113 of Document 7 (Japanese Unexamined Patent Publication No. 2013-151657).
- the cosmetic of the present invention includes oil-soluble gelling agents, organically modified clay minerals, antibacterial preservatives, bioactive ingredients, skin-beautifying ingredients, pH regulators, antioxidants, solvents, etc.
- Various components such as a chelating agent, a moisturizing component, a fragrance, and a deodorant can be used as long as the object of the present invention is not impaired.
- These optional cosmetic ingredients are the same as those disclosed by the applicants in Patent Document 7 (Japanese Unexamined Patent Publication No. 2013-151657).
- the external preparation composition according to the present invention is not particularly limited as long as it is a composition applied to the human body as a cosmetic or a pharmaceutical.
- Specific products of the present invention include skin cosmetics such as skin cleaning products, skin care products, makeup products, antiperspirant products, and UV protection products; hair cleaning products, hair styling products, etc. Hair cosmetics such as hair coloring products, hair nourishing products, hair rinsing products, hair conditioner products, and hair treatment products; bath cosmetics are exemplified.
- the pharmaceutical of the present invention include, but are not limited to, hair growth agents, hair growth agents, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and skin antiaging agents.
- the type, form and container of the external preparation composition according to the present invention are the same as those disclosed by the applicants in paragraphs 0230 to 0233 of Patent Document 5 (International Publication Patent WO2011 / 049248).
- the co-modified organopolysiloxane is particularly useful as a raw material for various make-up cosmetics, and the cosmetic according to the present invention is (A) the co-modified organopolysiloxane, (B) a powder or a colorant. , (C1) A make-up cosmetic containing a silicone oil liquid at 5 to 100 ° C. and (C2) an oil containing at least one selected from a hydrocarbon oil and a fatty acid ester oil is most suitable.
- Viscosity is a measured value at 25 ° C.
- M Me3SiO group
- D Me2SiO group
- DH MeHSiO group
- DR methyl group in D
- R 1 -C 2 H 4 Si (OSiMe 3 ) 3
- R 3 -C 16 H 33 .
- the product was a light brown viscous translucent liquid.
- Example 4 ⁇ Synthesis of covariant organopolysiloxane compound P4>
- the reactor was charged with 57.78 g of methylhydrogenpolysiloxane represented by the average composition formula MD 29 DH 7.3 M, 11.25 g of tristrimethylsiloxyvinylsilane, 27.43 g of hexadecene, and 3.54 g of diglycerin monoallyl ether.
- the temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours.
- Table 2 shows the results of preparing a body dispersion (slurry) and evaluating it according to the following evaluation criteria.
- ⁇ Slurry viscosity less than 2500 mPa ⁇ s
- ⁇ Slurry viscosity 2500 mPa ⁇ s or more
- ⁇ Slurry with fluidity cannot be produced
- a low-viscosity slurry could be formed using ethylhexyl palmitate, which is a typical fatty acid ester oil.
- the slurry could not be produced or became a highly viscous slurry, and sufficient powder dispersion performance could not be realized for fatty acid ester oil.
- the co-modified organopolysiloxanes according to the present invention can form a slurry having low viscosity and excellent stability over time even for decamethylcyclopentasiloxane, and are not suitable for silicone-based oils. It is also expected to have excellent powder dispersion performance with respect to silicone-based oils, and to improve powder dispersion stability in external preparation compositions and cosmetics using or using these oils.
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Abstract
[Problem] To provide a co-modified organopolysiloxane which has high affinity and compatibility with a wide range of cosmetic materials (in particular, non-silicone-based oils such as fatty acid ester oils), and, when used together with a powder, which can form a good and stable slurry without causing thickening or dispersion failure, and use of the co-modified organopolysiloxane. [Solution] A co-modified organopolysiloxane which is represented by structural formula (1) and has an HLB value of 0.5-2.0 and a viscosity of 200-1500 mPa·s, and use of the co-modified organopolysiloxane as a powder dispersant, etc. (In the formula: R1 represents a monovalent hydrocarbon group having 1-30 carbon atoms or a hydrogen atom; R2 represents a monovalent hydrocarbon group having 6-30 carbon atoms; L1 represents an organosilicon-containing organic group selected from a silylalkyl group having a carbosiloxy dendron structure and a group having a siloxane macromer structure; and Q represents a hydrophilic group which is a (poly)glycerol residue or a sugar alcohol residue).
Description
本発明は、分子内に特定のケイ素含有有機基、親水性基および長鎖アルキル基等の特定の炭化水素基を特定の比率で有し、かつ、一定のHLB値および粘度を有するため、多種多様な油剤との親和性に優れ、粉体処理剤として高い有用性を有する共変性オルガノポリシロキサンおよびその用途に関する。
The present invention has a specific hydrocarbon group such as a specific silicon-containing organic group, a hydrophilic group and a long-chain alkyl group in the molecule in a specific ratio, and has a constant HLB value and viscosity. The present invention relates to a co-modified organopolysiloxane having excellent affinity with various oil agents and having high usefulness as a powder treatment agent, and its use.
化粧品を含む外用剤組成物において、酸化チタン等の白色及び着色顔料、マイカ等の体質顔料に代表される各種粉体およびその油剤に対する粉体分散物が化粧料原料等として広く用いられており、その分散性、配合安定性および粉体を含む化粧料等の感触／機能を改善することを目的として、様々なシロキサン成分により粉体の表面処理を施した粉体が使用されている（例えば、特許文献１～６）。しかしながら、従来の粉体処理用シロキサンは、その性能が不十分であり、本件出願人は、分子内にカルボシロキシデンドロン構造等を有する基、グリセリン誘導体等の親水性基およびアルキル基を持ち、低分子量かつ低粘度の共変性オルガノポリシロキサン共重合体およびその粉体処理剤としての使用を提案している（特許文献７）。
In external preparation compositions including cosmetics, various powders typified by white and colored pigments such as titanium oxide, extender pigments such as mica, and powder dispersions for oils thereof are widely used as raw materials for cosmetics. For the purpose of improving the dispersibility, compounding stability, and feel / function of cosmetics containing powders, powders having been surface-treated with various siloxane components are used (for example,). Patent Documents 1 to 6). However, the performance of the conventional siloxane for powder treatment is insufficient, and the applicant has a group having a carbosiloxydendron structure or the like in the molecule, a hydrophilic group such as a glycerin derivative, and an alkyl group, and the performance is low. We have proposed the use of a co-modified organopolysiloxane copolymer having a molecular weight and low viscosity as a powder treatment agent thereof (Patent Document 7).
一方、特許文献７に具体的に開示された共変性オルガノポリシロキサンは、従来のシロキサン成分に比べて、高度な粉体分散性能を実現するものであるが、一部の低ＨＬＢ領域で油剤との粉体分散物を形成させた場合に、経時での増粘や流動性の低下等が起きる場合があり、その経時安定性に改善の余地を残している。これに加えて、近年、化粧料等の処方設計の自由度をさらに改善する見地から、より多様な油剤に対しても高度な親和性を有し、経時安定性に優れた粉体分散物を形成可能な共変性オルガノポリシロキサンが市場において求められている。
On the other hand, the co-modified organopolysiloxane specifically disclosed in Patent Document 7 realizes a higher powder dispersion performance than the conventional siloxane component, but it can be used as an oil agent in a part of the low HLB region. When the powder dispersion of No. 1 is formed, thickening and decrease in fluidity over time may occur, leaving room for improvement in its stability over time. In addition to this, in recent years, from the viewpoint of further improving the degree of freedom in formulation design of cosmetics, etc., we have created powder dispersions that have a high affinity for a wider variety of oils and have excellent stability over time. Formable co-modified organopolysiloxanes are sought after in the market.
本発明は、上記課題を解決すべくなされたものであり、幅広い化粧品原料(特に種類の異なる油剤)との親和性および相溶性に優れ、粉体と併用した場合に、増粘や分散不良を起こし難く、良好かつ安定なスラリーを形成できる共変性オルガノポリシロキサンを提供することを目的とする。また、本発明は、該オルガノポリシロキサンを含有してなる粉体処理剤、当該粉体処理剤によって表面処理された粉体、該共変性オルガノポリシロキサン共重合体を含有する粉体組成物、さらに、油剤を含有してなる油中粉体分散物、および、これらを含有してなる外用剤組成物、特にメークアップ化粧料およびその製造方法を提供することを目的とする。
The present invention has been made to solve the above problems, and has excellent affinity and compatibility with a wide range of cosmetic raw materials (particularly different types of oils), and when used in combination with powder, it causes thickening and poor dispersion. It is an object of the present invention to provide a co-modified organopolysiloxane that is difficult to cause and can form a good and stable slurry. Further, the present invention comprises a powder treatment agent containing the organopolysiloxane, a powder surface-treated with the powder treatment agent, and a powder composition containing the co-modified organopolysiloxane copolymer. Furthermore, it is an object of the present invention to provide a powder dispersion in oil containing an oil agent, and an external preparation composition containing these, particularly a make-up cosmetic and a method for producing the same.
鋭意検討の結果、本発明者らは、そのHLBが０．５～２．０の範囲であり、２５℃における粘度が２００～１５００ｍPa・ｓの範囲にあり、分子内に、特定の親水性基（Q）、C6～３０の長鎖炭化水素基（R2）、および、カルボシロキシデンドロン構造を有するシリルアルキル基およびシロキサンマクロモノマー構造を有する基から選ばれる有機ケイ素含有有機基（L1）を特定の比率で側鎖部分に有する、直鎖状かつ比較的低重合度の共変性オルガノポリシロキサンにより、上記課題を解決可能であることを見出し、本発明に到達した。また、当該共変性オルガノポリシロキサンを含有する粉体処理剤、粉体組成物、さらに、油剤を含有してなる油中粉体分散物、および、これらを含有してなる外用剤組成物、特にメークアップ化粧料およびその製造方法により上記課題を解決できることを見出し、本発明に到達した。なお、本発明に係る共変性オルガノポリシロキサンは、シリコーンオイルだけでなく非シリコーン系の有機油剤（例えば、炭化水素油および脂肪酸エステル油）に対しても優れた親和性および相溶性を有するため、異種の油剤を併用し、かつ、粉体を含む化粧料等の外用剤組成物に対して、特に好適に使用できる。
As a result of diligent studies, the present inventors have an HLB in the range of 0.5 to 2.0, a viscosity at 25 ° C. in the range of 200 to 1500 mPa · s, and a specific hydrophilic group in the molecule. (Q), C6 to 30 long-chain hydrocarbon groups (R2), and organic silicon-containing organic groups (L1) selected from groups having a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure are specified. We have found that the above-mentioned problems can be solved by a linear and relatively low-polymerization co-modified organopolysiloxane having a ratio in the side chain portion, and have reached the present invention. Further, a powder treatment agent and a powder composition containing the co-modified organopolysiloxane, a powder dispersion in oil containing an oil agent, and an external preparation composition containing these, in particular. We have found that the above-mentioned problems can be solved by a make-up cosmetic and a method for producing the same, and have reached the present invention. Since the co-modified organopolysiloxane according to the present invention has excellent affinity and compatibility not only with silicone oil but also with non-silicone organic oils (for example, hydrocarbon oil and fatty acid ester oil). It can be particularly preferably used for external preparation compositions such as cosmetics containing powders and in combination with different kinds of oils.
本発明により、幅広い化粧品原料(特に種類の異なる油剤)との親和性および相溶性に優れ、粉体と併用した場合に、増粘や分散不良を起こし難く、良好かつ安定なスラリーを形成できる共変性オルガノポリシロキサンを提供することができる。また、本発明により、該オルガノポリシロキサンを含有してなる粉体処理剤、当該粉体処理剤によって表面処理された粉体、該共変性オルガノポリシロキサン共重合体を含有する粉体組成物、さらに、油剤を含有してなる油中粉体分散物、および、これらを含有してなる外用剤組成物、特にメークアップ化粧料、その製造方法が提供される。
According to the present invention, it has excellent affinity and compatibility with a wide range of cosmetic raw materials (particularly different types of oils), and when used in combination with powder, it is less likely to cause thickening or dispersion failure, and a good and stable slurry can be formed. A modified organopolysiloxane can be provided. Further, according to the present invention, a powder treatment agent containing the organopolysiloxane, a powder surface-treated with the powder treatment agent, and a powder composition containing the co-modified organopolysiloxane copolymer. Further, a powder dispersion in oil containing an oil agent and an external preparation composition containing these, particularly a make-up cosmetic, and a method for producing the same are provided.
以下、本発明の共変性オルガノポリシロキサン、その各種処理剤（界面活性剤または表面処理剤）としての使用、特に粉体処理剤としての使用および化粧料原料としての使用について、詳細に説明する。また、本発明の共変性オルガノポリシロキサンを用いた油中粉体分散体、外用剤、好適には化粧料、特に好適にはメークアップ化粧料について詳細に説明する。なお、本発明の共変性オルガノポリシロキサンは、上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）および特許文献７（特開２０１３－１５１６５７号公報）に記載された共変性オルガノポリシロキサンと共通の用途に適用することが可能であり、これらの特許文献に開示された共変性オルガノポリシロキサンの一部または全部を置き換えて使用することができる。さらに、これらの特許文献に開示された化粧料等の剤形、種類および処方例について、そこに使用される共変性オルガノポリシロキサンの一部または全部を本発明に係る共変性オルガノポリシロキサンで置き換えることで、化粧料、粉体分散物、乳化物等を提供することができ、本発明はそのような処方設計を強く教示するものである。
Hereinafter, the co-modified organopolysiloxane of the present invention, its use as various treatment agents (surfactants or surface treatment agents), particularly its use as a powder treatment agent and its use as a cosmetic raw material will be described in detail. Further, a powder dispersion in oil using the co-modified organopolysiloxane of the present invention, an external preparation, preferably a cosmetic, and particularly preferably a make-up cosmetic will be described in detail. The co-modified organopolysiloxane of the present invention is the same as the co-modified organopolysiloxane described in Patent Document 5 (International Publication Patent WO2011 / 049248A) and Patent Document 7 (Japanese Patent Laid-Open No. 2013-151657). It can be applied to common uses, and can be used by replacing a part or all of the co-modified organopolysiloxane disclosed in these patent documents. Further, with respect to the dosage forms, types and formulation examples of cosmetics and the like disclosed in these patent documents, a part or all of the co-modified organopolysiloxane used therein is replaced with the co-modified organopolysiloxane according to the present invention. Thereby, cosmetics, powder dispersions, emulsions and the like can be provided, and the present invention strongly teaches such a formulation design.
本発明に係る共変性オルガノポリシロキサンは、後述する構造式（１）で表される、トリメチルシロキシ末端を有する鎖状ポリシロキサンであり、その側鎖部位に、カルボシロキシデンドロン構造を有するシリルアルキル基およびシロキサンマクロモノマー構造を有する基から選ばれる有機ケイ素含有有機基（L1）、特定の親水性基（Q）、炭素原子数６～３０の長鎖炭化水素基（R2）を特定の比率で有し、かつ、そのＨＬＢが０．５～２．０の範囲であり、２５℃における粘度が２００～１５００ｍPa・ｓの範囲にあることを特徴とする。
The co-modified organopolysiloxane according to the present invention is a chain polysiloxane having a trimethylsiloxy terminal represented by the structural formula (1) described later, and a silylalkyl group having a carbosiloxydendron structure at the side chain site thereof. And an organic silicon-containing organic group (L1) selected from groups having a siloxane macromonomer structure, a specific hydrophilic group (Q), and a long-chain hydrocarbon group (R2) having 6 to 30 carbon atoms in a specific ratio. Moreover, the HLB is in the range of 0.5 to 2.0, and the viscosity at 25 ° C. is in the range of 200 to 1500 mPa · s.
本発明において、親水性親油性バランス（ＨＬＢ）の値とは、「（親水基部分の総分子量／総分子量）×２０」により定義される値であり、本発明の共変性オルガノポリシロキサンにあっては、その値が０．５～２．０の範囲であることが必要であり、特に粉体分散剤としての性能の見地から、１．１～２．０の範囲であってよく、１．５～２．０の範囲であることが特に好ましい。後述する構造式（１）において、ａ～ｄの値、特に親水性基（Ｑ）の結合数に影響するｃの値は、分子全体のＨＬＢ値が前記範囲を満たす値であることが必要である。
In the present invention, the value of the hydrophilic lipophilic balance (HLB) is a value defined by "(total molecular weight of hydrophilic group portion / total molecular weight) x 20", and is in the co-modified organopolysiloxane of the present invention. Therefore, the value needs to be in the range of 0.5 to 2.0, and may be in the range of 1.1 to 2.0, particularly from the viewpoint of performance as a powder dispersant. It is particularly preferably in the range of .5 to 2.0. In the structural formula (1) described later, the values of a to d, particularly the value of c that affects the number of bonds of the hydrophilic group (Q), need to be a value in which the HLB value of the entire molecule satisfies the above range. be.
ＨＬＢの値が前記範囲外、特に、ＨＬＢの値が前記下限未満であって、分子内の親水基（Ｑ）の含有量が少ない場合、構造式（１）で表される共変性オルガノポリシロキサンであっても、固体表面を十分に被覆することができず、経時でスラリーが増粘傾向になるなど、粉体処理剤としての性能が不十分になる場合がある。一方、ＨＬＢの値が２．０よりも大きい、つまり分子内の親水基の含有量が多くなる場合、本発明に係る親水基（Ｑ）、好適にはジグリセリン誘導体基含有有機基や糖アルコール変性基等は、多数の水酸基を有しているので、水素結合による凝集力によって、共変性オルガノポリシロキサン自体の粘度が増大する傾向があり、粉体処理剤としての使用の際に、その取り扱い作業性が不十分となる場合がある。
When the HLB value is outside the above range, particularly when the HLB value is less than the lower limit and the content of the hydrophilic group (Q) in the molecule is small, the co-modified organopolysiloxane represented by the structural formula (1). Even so, the solid surface cannot be sufficiently coated, and the slurry tends to thicken over time, and the performance as a powder treatment agent may be insufficient. On the other hand, when the HLB value is larger than 2.0, that is, the content of the hydrophilic group in the molecule is large, the hydrophilic group (Q) according to the present invention, preferably a diglycerin derivative group-containing organic group or sugar alcohol. Since a modifying group or the like has a large number of hydroxyl groups, the viscosity of the co-modified organopolysiloxane itself tends to increase due to the cohesive force due to hydrogen bonding, and its handling when used as a powder treatment agent. Workability may be insufficient.
上記の通り、本発明に係る共変性オルガノポリシロキサンは、その粉体処理剤としての取り扱い作業性の見地から、２５℃における粘度が２００～１５００ｍPa・ｓの範囲にあることが必要であり、特に、非シリコーン系の有機油剤（例えば、炭化水素油および脂肪酸エステル油）に対する親和性の見地から、その粘度が３００～１４５０ｍPa・ｓの範囲が好ましく、７００～１４５０ｍPa・ｓの範囲にあることが特に好ましい。仮に、共変性オルガノポリシロキサンが前記のＨＬＢを有し、かつ、特定の親水性基、有機ケイ素含有有機基および炭素原子数６～３０の一価炭化水素基を備えていても、その粘度が前記上限を超えると、粉体処理剤としての取り扱い作業性が低下し、特に、非シリコーン系の有機油剤（例えば、炭化水素油および脂肪酸エステル油）を用いて粉体分散物を作成する際の作業効率および分散性が不十分となるほか、得られた粉体分散物（特に、油中粉体分散物であるスラリー）が経時的に増粘したり、粉体の分散が不十分であったりして化粧料原料としての使用が困難になるほか、条件によって、全く粉体分散物が調製できない場合がある。
As described above, the co-modified organopolysiloxane according to the present invention needs to have a viscosity at 25 ° C. in the range of 200 to 1500 mPa · s from the viewpoint of handling workability as a powder treatment agent, and in particular. From the viewpoint of affinity for non-silicone organic oils (for example, hydrocarbon oils and fatty acid ester oils), the viscosity is preferably in the range of 300 to 1450 mPa · s, and particularly preferably in the range of 700 to 1450 mPa · s. preferable. Even if the co-modified organopolysiloxane has the above-mentioned HLB and has a specific hydrophilic group, an organic silicon-containing organic group, and a monovalent hydrocarbon group having 6 to 30 carbon atoms, its viscosity is high. If the upper limit is exceeded, the handling workability as a powder treatment agent deteriorates, and in particular, when preparing a powder dispersion using a non-silicone-based organic oil agent (for example, a hydrocarbon oil and a fatty acid ester oil). In addition to insufficient work efficiency and dispersibility, the obtained powder dispersion (particularly, the slurry which is a powder dispersion in oil) thickens over time, and the dispersion of the powder is insufficient. This makes it difficult to use as a raw material for cosmetics, and depending on the conditions, it may not be possible to prepare a powder dispersion at all.
なお、共変性オルガノポリシロキサンの粘度は、親水性基（Ｑ）の種類、含有量および一般式（１）における各ジオルガノシロキシ単位の重合度ｎ１～ｎ４およびその和（ｎ１＋ｎ２＋ｎ３＋ｎ４）の影響を大きく受けるため、構造式（１）におけるｎ１～ｎ４の値は、上記の粘度範囲を充足する数である必要があり、特に好適には、（ｎ１＋ｎ２＋ｎ３＋ｎ４）の範囲が８～２５であり、ｎ１が３～１０であり、ｎ２が１～１０であり、ｎ３が０．１～１０であり、ｎ４が０．５～２．０であることが特に好ましい。
The viscosity of the co-modified organopolysiloxane is greatly affected by the type and content of the hydrophilic group (Q) and the degree of polymerization n1 to n4 of each diorganosiloxy unit in the general formula (1) and the sum thereof (n1 + n2 + n3 + n4). Therefore, the values of n1 to n4 in the structural formula (1) need to be numbers that satisfy the above viscosity range, and particularly preferably, the range of (n1 + n2 + n3 + n4) is 8 to 25, and n1 is 3. It is particularly preferable that n2 is 1 to 10, n3 is 0.1 to 10, and n4 is 0.5 to 2.0.
本発明に係る共変性オルガノポリシロキサンは、下記構造式（１）：
（１）
で表される。 The covariant organopolysiloxane according to the present invention has the following structural formula (1):
(1)
It is represented by.
で表される。 The covariant organopolysiloxane according to the present invention has the following structural formula (1):
It is represented by.
式中、Ｒ１は置換もしくは非置換の炭素原子数１～３０の一価炭化水素基または水素原子であり、その他のＲ２、Ｌ１、およびＱに該当する基を含まず、工業的にはメチル基またはフェニル基であることが好ましい。
In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms, and does not contain other groups corresponding to R 2 , L 1 , and Q, and is industrially used. Is preferably a methyl group or a phenyl group.
Ｒ２は、炭素原子数６～３０の、置換もしくは非置換の、直鎖状もしくは分岐状の一価炭化水素基であり、特に炭化水素系油剤（化粧料原料）等の非シリコーン系油剤との親和性を改善することができる。好適には、Ｒ２は、炭素原子数６～３０のアルキル基であり、ヘキシル基，ヘプチル基，オクチル基，デシル基，ドデシル基、ウンデシル、ヘキサデシル基等が例示され、特に、炭素原子数８～２０のアルキル基が好ましい。
R2 is a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, and in particular, with a non-silicone oil such as a hydrocarbon oil (cosmetic raw material). Affinity can be improved. Preferably, R 2 is an alkyl group having 6 to 30 carbon atoms, and examples thereof include a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, undecyl, and a hexadecyl group, and in particular, the number of carbon atoms is 8. Up to 20 alkyl groups are preferred.
Ｌ１は、カルボシロキシデンドロン構造を有するシリルアルキル基およびシロキサンマクロモノマー構造を有する基から選ばれる有機ケイ素含有有機基であり、具体的には、
ｉ＝１のときの下記一般式（２）：
（２）
（式中、Ｒ１は前記同様の基であり、ＲＣは炭素原子数１～６のアルキル基またはフェニル基であり、Ｚは二価の有機基である。ｉはＬｉで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がｃのとき１～ｃの整数であり、階層数ｃは１～１０の整数であり、Ｌｉ＋１はｉがｃ未満のときは該シリルアルキル基であり、ｉ＝ｃのときはメチル基またはフェニル基である。ａｉは０～３の範囲の数である）で示されるシロキサンデンドロン構造を有するシリルアルキル基、
下記一般式（２´）：
（２´）
（式中、Ｒ１１はそれぞれ独立して置換若しくは非置換の炭素原子数１～３０の一価炭化水素基、水酸基又は水素原子であり、Ｒ１１のうち少なくとも一つは前記一価炭化水素基である。ｔは２～１０の範囲の数であり、ｒは１～５００の範囲の数である）で示される鎖状のオルガノシロキサン基、および
下記一般式（２´´）：
（２´´）
（式中、Ｒ１１及びｒは上記のとおりである）で示される鎖状のオルガノシロキサン基から選ばれる１種以上の基である。 L 1 is an organosilicon-containing organic group selected from a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure, and specifically, L 1 is an organosilicon-containing organic group.
The following general formula (2) when i = 1:
(2)
(In the formula, R 1 is the same group as described above, RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, Z is a divalent organic group, and i is a silyl represented by Li. It indicates the layer of the alkyl group, and when the number of layers which is the number of repetitions of the silylalkyl group is c, it is an integer of 1 to c, the number of layers c is an integer of 1 to 10, and Li + 1 is i less than c. When it is the silylalkyl group, when i = c, it is a methyl group or a phenyl group. Ai is a number in the range of 0 to 3), and a silylalkyl group having a siloxane dendron structure,
The following general formula (2'):
(2')
(In the formula, R 11 is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group. T is a number in the range of 2 to 10, r is a number in the range of 1 to 500), and the chain organosiloxane group represented by the following general formula (2 ′ ′) :.
(2')
(In the formula, R 11 and r are as described above), which is one or more groups selected from the chain-like organosiloxane groups.
ｉ＝１のときの下記一般式（２）：
（式中、Ｒ１は前記同様の基であり、ＲＣは炭素原子数１～６のアルキル基またはフェニル基であり、Ｚは二価の有機基である。ｉはＬｉで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がｃのとき１～ｃの整数であり、階層数ｃは１～１０の整数であり、Ｌｉ＋１はｉがｃ未満のときは該シリルアルキル基であり、ｉ＝ｃのときはメチル基またはフェニル基である。ａｉは０～３の範囲の数である）で示されるシロキサンデンドロン構造を有するシリルアルキル基、
下記一般式（２´）：
（式中、Ｒ１１はそれぞれ独立して置換若しくは非置換の炭素原子数１～３０の一価炭化水素基、水酸基又は水素原子であり、Ｒ１１のうち少なくとも一つは前記一価炭化水素基である。ｔは２～１０の範囲の数であり、ｒは１～５００の範囲の数である）で示される鎖状のオルガノシロキサン基、および
下記一般式（２´´）：
（式中、Ｒ１１及びｒは上記のとおりである）で示される鎖状のオルガノシロキサン基から選ばれる１種以上の基である。 L 1 is an organosilicon-containing organic group selected from a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure, and specifically, L 1 is an organosilicon-containing organic group.
The following general formula (2) when i = 1:
(In the formula, R 1 is the same group as described above, RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, Z is a divalent organic group, and i is a silyl represented by Li. It indicates the layer of the alkyl group, and when the number of layers which is the number of repetitions of the silylalkyl group is c, it is an integer of 1 to c, the number of layers c is an integer of 1 to 10, and Li + 1 is i less than c. When it is the silylalkyl group, when i = c, it is a methyl group or a phenyl group. Ai is a number in the range of 0 to 3), and a silylalkyl group having a siloxane dendron structure,
The following general formula (2'):
(In the formula, R 11 is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group. T is a number in the range of 2 to 10, r is a number in the range of 1 to 500), and the chain organosiloxane group represented by the following general formula (2 ′ ′) :.
(In the formula, R 11 and r are as described above), which is one or more groups selected from the chain-like organosiloxane groups.
Ｌ１で示される基は、同一であっても異なってもよい。例えば、カルボシロキシデンドロン構造を有するシリルアルキル基およびシロキサンマクロモノマー構造を有する基を同一分子内に有してもよく、シリルアルキル基にあっては分岐の程度(世代)が異なる有機ケイ素含有有機基の組み合わせであってよく、およびシロキサンマクロモノマー構造を有する基においては、重合度の異なる有機ケイ素含有有機基の組み合わせであってもよい。
The groups represented by L 1 may be the same or different. For example, a silylalkyl group having a carbosiloxydendron structure and a group having a siloxane macromonomer structure may be contained in the same molecule, and the silylalkyl group has an organic silicon-containing organic group having a different degree of branching (generation). And, in the group having a siloxane macromonomer structure, it may be a combination of organic silicon-containing organic groups having different degrees of polymerization.
Ｌ１で示される基はカルボシロキサンデンドリマー構造を有するシリルアルキル基であってよく、ｉ＝１のときの上記一般式（２）で示されるシリルアルキル基として定義される。該カルボシロキサンデンドリマー構造を有するシリルアルキル基は、カルボシロキサン単位がデンドリマー状に広がった構造を有しているため、線状あるいは単なる分岐状のポリシロキサン単位に比して、高撥水性を呈する官能基であり、親水性官能基由来の感触を損なうことなく、本願に係る共変性オルガノポリシロキサンに優れた界面活性剤、粉体処理剤を与えることができる。また、該カルボシロキサンデンドリマー構造を有するシリルアルキル基は、化学的に安定であるために幅広い化粧料配合成分と組み合わせて使用することができるという有利な特性を付与する官能基である。
The group represented by L 1 may be a silylalkyl group having a carbosiloxane dendrimer structure, and is defined as a silylalkyl group represented by the above general formula (2) when i = 1. Since the silylalkyl group having the carbosiloxane dendrimer structure has a structure in which the carbosiloxane unit spreads like a dendrimer, the functional group exhibiting high water repellency as compared with the linear or simply branched polysiloxane unit. It is a group, and an excellent surfactant and powder treatment agent can be provided to the co-modified organopolysiloxane according to the present application without impairing the feel derived from the hydrophilic functional group. Further, the silylalkyl group having a carbosiloxane dendrimer structure is a functional group that imparts an advantageous property that it can be used in combination with a wide range of cosmetic compounding ingredients because it is chemically stable.
一般式（２）において、ＲＣは炭素原子数１～６のアルキル基またはフェニル基であり、工業的には、メチル基又はフェニル基であることが好ましい。
In the general formula (2), RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, and industrially, it is preferably a methyl group or a phenyl group.
一般式（２）において、ｉはＬ１で示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がｃのとき１～ｃの整数であり、階層数ｃは１～１０の整数であり、Ｌｉ＋１はｉがｃ未満のときは該シリルアルキル基であり、ｉ＝ｃのときはメチル基またはフェニル基である。特に、ｉ＝ｃのときはメチル基であることが好ましい。
In the general formula (2), i indicates the layer of the silylalkyl group represented by L1, and when the number of layers, which is the number of repetitions of the silylalkyl group, is c, it is an integer of 1 to c, and the number of layers c is 1. It is an integer of ~ 10, and Li + 1 is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i = c. In particular, when i = c, it is preferably a methyl group.
階層数ｃは、工業的には１～３の整数であることが好適であり、より好適には、１または
２である。各階層数において、Ｌ１で示される基は以下のように表される。式中、Ｒ２お
よびＺは前記同様の基である。 Industrially, the number of layers c is preferably an integer of 1 to 3, and more preferably 1 or 2. In each layer number, the group represented by L1 is represented as follows. In the formula, R2 and Z are the same groups as described above.
２である。各階層数において、Ｌ１で示される基は以下のように表される。式中、Ｒ２お
よびＺは前記同様の基である。 Industrially, the number of layers c is preferably an integer of 1 to 3, and more preferably 1 or 2. In each layer number, the group represented by L1 is represented as follows. In the formula, R2 and Z are the same groups as described above.
階層数ｃ＝１である場合、Ｌ１は下記一般式（２－１）で示される。
（２－１）
When the number of layers c = 1, L1 is represented by the following general formula (2-1).
(2-1)
階層数ｃ＝２である場合、Ｌ１は下記一般式（２－２）で示される。
（２－２）
When the number of layers c = 2, L1 is represented by the following general formula (2-2).
(2-2)
式（２）において、ａｉは各々独立に０～３の範囲の数であり、階層数が１～３の場合における式（２－１）～（２－３）で示される構造において、ａ１，ａ２およびａ３は各々独立に０～３の範囲の数である。これらのａｉは特に０～１の範囲の数であることが好ましく、ａｉが０であることが特に好ましい。
In the formula (2), ai is a number in the range of 0 to 3 independently, and in the structure represented by the formulas (2-1) to (2-3) when the number of layers is 1 to 3, a1 and a1 a2 and a3 are independently numbers in the range 0-3. These ai are particularly preferably in the range of 0 to 1, and particularly preferably 0.
上式中、Ｚは、各々独立に２価の有機基であり、具体的には、ケイ素結合水素原子と、アルケニル基、アクリロキシ基、メタクリロキシ基等の不飽和炭化水素基を末端に有する官能基を付加反応させることにより形成される２価の有機基が挙げられるが、カルボシロキサンデンドリマー構造を有するシリルアルキル基の導入法に応じて、これらの官能基に限らず、適宜選択することができる。このような官能基は特許文献７等に多数開示されているが、本発明におけるＺは炭素原子数２～１０のアルキレン基であることが好ましく、エチレン基であることが最も好ましい。
In the above formula, Z is an independently divalent organic group, and specifically, a functional group having a silicon-bonded hydrogen atom and an unsaturated hydrocarbon group such as an alkenyl group, an acryloxy group, or a methacrylate group at the end. Examples thereof include a divalent organic group formed by the addition reaction of the above, and the group is not limited to these functional groups and can be appropriately selected depending on the method for introducing a silylalkyl group having a carbosiloxane dendrimer structure. Although many such functional groups are disclosed in Patent Document 7 and the like, Z in the present invention is preferably an alkylene group having 2 to 10 carbon atoms, and most preferably an ethylene group.
Ｌ１で示される基は、酸素またはアルキレン基を介して主鎖を構成するケイ素原子に結合するシロキサンマクロモノマー構造含有基であってよく、疎水性であり、一定の撥水性／親油性を呈する官能基であり、親水性官能基由来の感触を損なうことなく、本願に係るオルガノポリシロキサン共重合体に優れた界面活性剤、粉体処理剤を与えることができる。具体的には、Ｌ１で示される基は、上記一般式（２´）および一般式（２´´）で示される官能基であってよい。式中、Ｒ１１は工業的に特に好適には、メチル基，フェニル基又は水酸基が上げられ、Ｒ１１の一部がメチル基であり、一部が炭素原子数８～３０の長鎖アルキル基であるような形態も好適であるが、Ｒ１１の少なくとも一つはメチル基等の一価炭化水素基であり、ｔは２～１０の範囲の数であり、ｒは１～５００の範囲の数であり、各種油剤との相溶性の観点から、ｒは１～１００の範囲の数であることが好ましく、２～３０の範囲の数であることが特に好ましい。
The group represented by L 1 may be a siloxane macromonomer structure-containing group bonded to a silicon atom constituting the main chain via an oxygen or an alkylene group, is hydrophobic, and exhibits a certain water repellency / oil resistance. It is a functional group, and an excellent surfactant and powder treatment agent can be provided to the organopolysiloxane copolymer according to the present application without impairing the feel derived from the hydrophilic functional group. Specifically, the group represented by L 1 may be a functional group represented by the above general formula (2') and general formula (2''). In the formula, R 11 is industrially particularly preferably a long-chain alkyl group in which a methyl group, a phenyl group or a hydroxyl group is raised, a part of R 11 is a methyl group, and a part is a long-chain alkyl group having 8 to 30 carbon atoms. However, at least one of R 11 is a monovalent hydrocarbon group such as a methyl group, t is a number in the range of 2 to 10, and r is in the range of 1 to 500. It is a number, and from the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and particularly preferably a number in the range of 2 to 30.
Ｑは二価の連結基（Ｚ）を介してケイ素原子に結合した、下記構造式（３―１）～（３－２）：
（３－１）
（式中、Ｚは炭素原子数２～２２のアルキレン基または－Ｒ６－Ｃ（＝Ｏ）－Ｏ－Ｒ７－で示される２価の有機基（Ｒ６は炭素原子数２～２２のアルキレン基であり、Ｒ７はエチレン基、プロピレン基、メチルエチレン基又はヘキシレン基から選択される基）を表し、ｍは１又は２である）
（３－２）
（式中、Ｚは上記のとおりであり、ｍ’は０又は１である）
で表される糖アルコールを含有してなる親水性基、および、下記構造式（３－３）～（３－５）：
（３－３）
（式中、Ｗは水素原子または炭素原子数１～２０のアルキル基。）
（３－４）
（３－５）
で表される親水性単位から選択される少なくとも１種以上の親水性単位を含有してなる親水性基である。かかる親水性基であるＱは、本願に係る共変性オルガノポリシロキサンに親水性を付与する部分であり、一般的に、親水性化合物から誘導される官能基である。上記の通り定義されるＱは、部分的に分子鎖末端が炭化水素により封鎖されていても良い、一価以上のアルコール類、ポリエーテル系化合物、（ポリ）グリセリン系化合物、（ポリ）グリシジルエーテル系化合物、親水性糖類から誘導される官能基が好適に例示できる。 Q is bonded to a silicon atom via a divalent linking group (Z), and has the following structural formulas (3-1) to (3-2):
(3-1)
(In the formula, Z is an alkylene group having 2 to 22 carbon atoms or a divalent organic group represented by -R 6 -C (= O) -OR 7- (R 6 is a divalent organic group having 2 to 22 carbon atoms. It is an alkylene group, where R7 represents a group selected from an ethylene group, a propylene group, a methylethylene group or a hexylene group), and m is 1 or 2).
(3-2)
(In the formula, Z is as described above and m'is 0 or 1).
A hydrophilic group containing a sugar alcohol represented by the following, and the following structural formulas (3-3) to (3-5):
(3-3)
(In the formula, W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
(3-4)
(3-5)
A hydrophilic group containing at least one hydrophilic unit selected from the hydrophilic units represented by. The hydrophilic group Q is a portion that imparts hydrophilicity to the covariant organopolysiloxane according to the present application, and is generally a functional group derived from a hydrophilic compound. Q defined as described above has monohydric or higher alcohols, polyether compounds, (poly) glycerin compounds, and (poly) glycidyl ethers whose molecular chain ends may be partially blocked by hydrocarbons. A functional group derived from a system compound or a hydrophilic saccharide can be preferably exemplified.
（式中、Ｚは炭素原子数２～２２のアルキレン基または－Ｒ６－Ｃ（＝Ｏ）－Ｏ－Ｒ７－で示される２価の有機基（Ｒ６は炭素原子数２～２２のアルキレン基であり、Ｒ７はエチレン基、プロピレン基、メチルエチレン基又はヘキシレン基から選択される基）を表し、ｍは１又は２である）
（式中、Ｚは上記のとおりであり、ｍ’は０又は１である）
で表される糖アルコールを含有してなる親水性基、および、下記構造式（３－３）～（３－５）：
（式中、Ｗは水素原子または炭素原子数１～２０のアルキル基。）
で表される親水性単位から選択される少なくとも１種以上の親水性単位を含有してなる親水性基である。かかる親水性基であるＱは、本願に係る共変性オルガノポリシロキサンに親水性を付与する部分であり、一般的に、親水性化合物から誘導される官能基である。上記の通り定義されるＱは、部分的に分子鎖末端が炭化水素により封鎖されていても良い、一価以上のアルコール類、ポリエーテル系化合物、（ポリ）グリセリン系化合物、（ポリ）グリシジルエーテル系化合物、親水性糖類から誘導される官能基が好適に例示できる。 Q is bonded to a silicon atom via a divalent linking group (Z), and has the following structural formulas (3-1) to (3-2):
(In the formula, Z is an alkylene group having 2 to 22 carbon atoms or a divalent organic group represented by -R 6 -C (= O) -OR 7- (R 6 is a divalent organic group having 2 to 22 carbon atoms. It is an alkylene group, where R7 represents a group selected from an ethylene group, a propylene group, a methylethylene group or a hexylene group), and m is 1 or 2).
(In the formula, Z is as described above and m'is 0 or 1).
A hydrophilic group containing a sugar alcohol represented by the following, and the following structural formulas (3-3) to (3-5):
(In the formula, W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
A hydrophilic group containing at least one hydrophilic unit selected from the hydrophilic units represented by. The hydrophilic group Q is a portion that imparts hydrophilicity to the covariant organopolysiloxane according to the present application, and is generally a functional group derived from a hydrophilic compound. Q defined as described above has monohydric or higher alcohols, polyether compounds, (poly) glycerin compounds, and (poly) glycidyl ethers whose molecular chain ends may be partially blocked by hydrocarbons. A functional group derived from a system compound or a hydrophilic saccharide can be preferably exemplified.
本発明に係る共変性オルガノポリシロキサンは、その粉体処理剤としての特性、特に無機粉体の分散特性の観点から、上記構造式式（１）等において、Ｑが多価アルコール含有有機基であることが好ましく、（ポリ）グリセリン残基または糖アルコール残基であることが特に好ましい。粉体処理剤としての性能、特に、共変性オルガノポリシロキサンの全体粘度を抑制する見地から、Ｑは（ポリ）グリセリン系化合物から誘導されてなる親水性基であり、（ポリ）グリセリンから誘導されてなる親水性基であることが最も好ましい。具体的には、（ポリ）グリセリンモノアリルエーテル，（ポリ）グリセリルオイゲノールであって、モノグリセリン、ジグリセリン、トリグリセリンまたはテトラグリセリン構造を有する（ポリ）グリセリン系化合物から誘導されてなる親水性基が好適であり、ジグリセリン誘導体である親水性基が最適である。
In the co-modified organopolysiloxane according to the present invention, Q is a polyhydric alcohol-containing organic group in the above structural formula (1) and the like from the viewpoint of the characteristics as a powder treatment agent, particularly the dispersion characteristics of inorganic powder. It is preferably present, and particularly preferably a (poly) glycerin residue or a sugar alcohol residue. From the viewpoint of suppressing the overall viscosity of the co-modified organopolysiloxane, Q is a hydrophilic group derived from a (poly) glycerin-based compound, and is derived from (poly) glycerin. Most preferably, it is a hydrophilic group. Specifically, it is a (poly) glycerin monoallyl ether, (poly) glyceryl eugenol, and is a hydrophilic group derived from a (poly) glycerin-based compound having a monoglycerin, diglycerin, triglycerin or tetraglycerin structure. Is preferable, and a hydrophilic group which is a diglycerin derivative is most suitable.
前記ジグリセリン誘導体基は、より好適には、下記構造式（５）：
－Ｒ５－Ｏ－Ｘｍ－Ｈ （５）
で表わされるジグリセリン誘導体基である。
式中、Ｒ５はオキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を含有しない二価有機基であり、炭素原子数２～１０のアルキレン基であることが好ましい。Ｘは前記の上記構造式（３－３）～（３－５）で表される親水性単位（＝グリセリン単位）から選択されるいずれかの親水性単位であり、ｍは当該グリセリン単位の繰り返し数であり、平均して１．５～２．４の範囲の数である。なお、各グリセリン単位の繰り返し数の平均値が１．１～２．９の範囲にあり、好適には繰り返し数の平均値が１．５～２．４の範囲であり、より好適には、１．８～２．２の範囲であり、最も好適には平均２である。すなわち、Ｑであるグリセリン誘導体基は、ジグリセリン誘導体基を主として含有する。ここで、ジグリセリン誘導体基は、グリセリン単位の繰り返し構造が分岐を有しないことが好ましいが、その一部がポリグリセロール基またはポリグリシジルエーテル基のように、一部に分岐構造を有する構造であっても良い。 More preferably, the diglycerin derivative group has the following structural formula (5):
-R 5 -OX m -H (5)
It is a diglycerin derivative group represented by.
In the formula, R5 is a divalent organic group containing no oxyalkylene structure having an average value of 2 or more repetitions of the oxyalkylene unit, and is preferably an alkylene group having 2 to 10 carbon atoms. X is any hydrophilic unit selected from the hydrophilic units (= glycerin units) represented by the above structural formulas (3-3) to (3-5), and m is a repetition of the glycerin units. It is a number, which is a number in the range of 1.5 to 2.4 on average. The average value of the number of repetitions for each glycerin unit is in the range of 1.1 to 2.9, preferably the average value of the number of repetitions is in the range of 1.5 to 2.4, and more preferably. It ranges from 1.8 to 2.2, most preferably an average of 2. That is, the glycerin derivative group which is Q mainly contains a diglycerin derivative group. Here, the diglycerin derivative group preferably has a structure in which the repeating structure of the glycerin unit does not have a branch, but a part thereof has a branched structure such as a polyglycerol group or a polyglycidyl ether group. May be.
－Ｒ５－Ｏ－Ｘｍ－Ｈ （５）
で表わされるジグリセリン誘導体基である。
式中、Ｒ５はオキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を含有しない二価有機基であり、炭素原子数２～１０のアルキレン基であることが好ましい。Ｘは前記の上記構造式（３－３）～（３－５）で表される親水性単位（＝グリセリン単位）から選択されるいずれかの親水性単位であり、ｍは当該グリセリン単位の繰り返し数であり、平均して１．５～２．４の範囲の数である。なお、各グリセリン単位の繰り返し数の平均値が１．１～２．９の範囲にあり、好適には繰り返し数の平均値が１．５～２．４の範囲であり、より好適には、１．８～２．２の範囲であり、最も好適には平均２である。すなわち、Ｑであるグリセリン誘導体基は、ジグリセリン誘導体基を主として含有する。ここで、ジグリセリン誘導体基は、グリセリン単位の繰り返し構造が分岐を有しないことが好ましいが、その一部がポリグリセロール基またはポリグリシジルエーテル基のように、一部に分岐構造を有する構造であっても良い。 More preferably, the diglycerin derivative group has the following structural formula (5):
-R 5 -OX m -H (5)
It is a diglycerin derivative group represented by.
In the formula, R5 is a divalent organic group containing no oxyalkylene structure having an average value of 2 or more repetitions of the oxyalkylene unit, and is preferably an alkylene group having 2 to 10 carbon atoms. X is any hydrophilic unit selected from the hydrophilic units (= glycerin units) represented by the above structural formulas (3-3) to (3-5), and m is a repetition of the glycerin units. It is a number, which is a number in the range of 1.5 to 2.4 on average. The average value of the number of repetitions for each glycerin unit is in the range of 1.1 to 2.9, preferably the average value of the number of repetitions is in the range of 1.5 to 2.4, and more preferably. It ranges from 1.8 to 2.2, most preferably an average of 2. That is, the glycerin derivative group which is Q mainly contains a diglycerin derivative group. Here, the diglycerin derivative group preferably has a structure in which the repeating structure of the glycerin unit does not have a branch, but a part thereof has a branched structure such as a polyglycerol group or a polyglycidyl ether group. May be.
最も好適には、ジグリセリン誘導体基含有有機基は、下記一般式（５－１）
（５－１）
（式中、Ｒ５はオキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を有しない二価有機基を表す）、又は、下記一般式（５－２）
（５－２）
（式中、Ｒ５は上記のとおりである）で表わされるジグリセリン誘導体基含有有機基である。 Most preferably, the diglycerin derivative group-containing organic group has the following general formula (5-1).
(5-1)
(In the formula, R 5 represents a divalent organic group having no oxyalkylene structure in which the average value of the number of repetitions of the oxyalkylene unit is 2 or more), or the following general formula (5-2).
(5-2)
( In the formula, R5 is as described above) is a diglycerin derivative group-containing organic group.
（式中、Ｒ５はオキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を有しない二価有機基を表す）、又は、下記一般式（５－２）
（式中、Ｒ５は上記のとおりである）で表わされるジグリセリン誘導体基含有有機基である。 Most preferably, the diglycerin derivative group-containing organic group has the following general formula (5-1).
(In the formula, R 5 represents a divalent organic group having no oxyalkylene structure in which the average value of the number of repetitions of the oxyalkylene unit is 2 or more), or the following general formula (5-2).
( In the formula, R5 is as described above) is a diglycerin derivative group-containing organic group.
本発明に係る本発明の共変性オルガノポリシロキサンにおいて、ジグリセリン誘導体基含有有機基は、ジグリセリンモノアリルエーテル，ジグリセリルオイゲノールから誘導されてなる親水性基が好適である。最も好ましいものは、式（５）において、ｍ＝２であるジグリセリン誘導体基の純度が９８質量％を超える純品である。
In the co-modified organopolysiloxane of the present invention according to the present invention, the diglycerin derivative group-containing organic group is preferably a hydrophilic group derived from diglycerin monoallyl ether or diglyceryl eugenol. The most preferable is a pure product having a purity of the diglycerin derivative group having m = 2 in the formula (5) exceeding 98% by mass.
Ｑである糖アルコール含有有機基は、糖アルコール含有有機基としては、構造式（３－１）において、Ｚがプロピレン基であり、ｍ＝１である場合が特に好ましい。同様に、糖アルコール含有有機基として、構造式（３－２）において、Ｚがプロピレン基であり、ｍ’＝０である場合が特に好ましい。この場合の糖アルコール含有有機基は構造式（３－１）又は（３－２）に対応して、構造式：－Ｃ3Ｈ6－ＯＣＨ２[ＣＨ（ＯＨ）]３ＣＨ２ＯＨ、
又は、構造式：－Ｃ3Ｈ6－ＯＣＨ｛ＣＨ（ＯＨ）ＣＨ２ＯＨ｝２で示されるキシリトール残基である。 As the sugar alcohol-containing organic group Q, it is particularly preferable that Z is a propylene group and m = 1 in the structural formula (3-1) as the sugar alcohol-containing organic group. Similarly, as the sugar alcohol-containing organic group, it is particularly preferable that Z is a propylene group and m'= 0 in the structural formula (3-2). The sugar alcohol-containing organic group in this case corresponds to the structural formula (3-1) or (3-2), and the structural formula: -C 3 H 6 -OCH 2 [CH (OH)] 3 CH 2 OH,
Alternatively, it is a xylitol residue represented by the structural formula: -C 3 H 6 -OCH {CH (OH) CH 2 OH} 2 .
又は、構造式：－Ｃ3Ｈ6－ＯＣＨ｛ＣＨ（ＯＨ）ＣＨ２ＯＨ｝２で示されるキシリトール残基である。 As the sugar alcohol-containing organic group Q, it is particularly preferable that Z is a propylene group and m = 1 in the structural formula (3-1) as the sugar alcohol-containing organic group. Similarly, as the sugar alcohol-containing organic group, it is particularly preferable that Z is a propylene group and m'= 0 in the structural formula (3-2). The sugar alcohol-containing organic group in this case corresponds to the structural formula (3-1) or (3-2), and the structural formula: -C 3 H 6 -OCH 2 [CH (OH)] 3 CH 2 OH,
Alternatively, it is a xylitol residue represented by the structural formula: -C 3 H 6 -OCH {CH (OH) CH 2 OH} 2 .
構造式（１）において、各ジオルガノシロキシ単位の平均重合度を表すｎ１～ｎ４について、（ｎ１＋ｎ２＋ｎ３＋ｎ４）が２～５０の範囲の数であり、好適には５～４０であり、特に好適には８～２５である。ｎ１は０～２０の範囲の数であり、より好適には３～１０である。ｎ２は１～１０の範囲の数であり、より好適には１．0～５．０である。ｎ３は０．１～１０の範囲の数であり、より好適には０．１～５である。ｎ４は０．３～２．５の範囲の数であり、より好適には０．５～２．０である。また、ｎ４は、親水性基Ｑの含有量に影響するので、ｎ４は、分子全体のＨＬＢ値が０．５～２．０となる範囲、より好適には１．５～２．０となる範囲の数の数であることが特に好ましい。
In the structural formula (1), for n1 to n4 representing the average degree of polymerization of each diorganosiloxy unit, (n1 + n2 + n3 + n4) is a number in the range of 2 to 50, preferably 5 to 40, and particularly preferably. It is 8 to 25. n1 is a number in the range of 0 to 20, more preferably 3 to 10. n2 is a number in the range of 1-10, more preferably 1.0-5.0. n3 is a number in the range of 0.1 to 10, and more preferably 0.1 to 5. n4 is a number in the range of 0.3 to 2.5, more preferably 0.5 to 2.0. Further, since n4 affects the content of the hydrophilic group Q, n4 is in the range where the HLB value of the entire molecule is 0.5 to 2.0, and more preferably 1.5 to 2.0. Especially preferred is the number of ranges.
本発明に係る共変性オルガノポリシロキサンは、Ｓｉ－Ｈ等の反応性官能基を有するオルガノポリシロキサンに対して、分子鎖の片末端に１個の炭素－炭素二重結合を有する有機ケイ素含有有機基（例えば、前記のシリルアルキル基）を有する化合物、アルケニル基等の反応性官能基を有する親水性化合物（例えばジグリセリンモノアリルエーテル等）および、分子鎖の片末端に炭素－炭素二重結合を有する不飽和長鎖炭化水素化合物を付加反応させることにより得ることができる。当該反応は、Ｓｉ－Ｈ等の反応性官能基を有するオルガノポリシロキサンに対して、前記の原料を多段階で付加反応させることが好ましく、反応のコントロール、純度および収率の点から、ヒドロシリル化反応触媒の存在下において付加反応させることが好ましい。また、付加反応により得られた共変性オルガノポリシロキサンの粗製品は、水素化触媒の存在下、溶媒もしくは無溶媒中で水素添加反応による無臭化処理を行って精製しても良く、酸性物質による低臭化処理を行っても良い。さらに、本発明に係る共変性オルガノポリシロキサンは、アルケニル基等の反応性官能基を有する親水性化合物との混合物として得られても良い。
The co-modified organopolysiloxane according to the present invention is an organic silicon-containing organic having one carbon-carbon double bond at one end of the molecular chain with respect to the organopolysiloxane having a reactive functional group such as Si—H. A compound having a group (for example, the above-mentioned silylalkyl group), a hydrophilic compound having a reactive functional group such as an alkenyl group (for example, diglycerin monoallyl ether, etc.), and a carbon-carbon double bond at one end of the molecular chain. It can be obtained by carrying out an addition reaction with an unsaturated long-chain hydrocarbon compound having. In the reaction, it is preferable to add the above-mentioned raw materials to an organopolysiloxane having a reactive functional group such as Si—H in multiple steps, and hydrosilylation is performed from the viewpoint of reaction control, purity and yield. It is preferable to carry out an addition reaction in the presence of a reaction catalyst. Further, the crude product of the co-modified organopolysiloxane obtained by the addition reaction may be purified by deodorizing treatment by hydrogenation reaction in the presence of a hydrogenation catalyst in a solvent or no solvent, and may be purified by an acidic substance. A low odor treatment may be performed. Further, the co-modified organopolysiloxane according to the present invention may be obtained as a mixture with a hydrophilic compound having a reactive functional group such as an alkenyl group.
本発明に係る共変性オルガノポリシロキサンの合成にあたっては、出願人らが上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）段落０１１０～０１２２により開示した反応、精製、および酸性物質による低臭化処理等と共通の方法を採用することができる。特に、共変性オルガノポリシロキサンの実質的な無臭化が可能であることから、２５℃で固体であり、水溶性であり、かつ、５０ｇをイオン交換水１Ｌに溶解させたときの水溶液の２５℃におけるｐＨが４以下であることを特徴とする１種類以上の酸性無機塩（好適には、硫酸水素ナトリウム等）で処理することが好ましい。例えば、上記の通り（１）ヒドロシリル化反応により合成された共変性オルガノポリシロキサン組成物の反応系（例えば、フラスコなどの反応容器）中に、上記の酸性無機塩を添加して、撹拌する分解処理、（２）酸性無機塩と水若しくは酸性無機塩と水と親水性溶媒を添加して、撹拌する加水分解処理などを意味する。酸性無機塩を用いた処理工程は、水および／または親水性媒体の存在下に行うことが好ましい。
In synthesizing the co-modified organopolysiloxane according to the present invention, the reaction, purification, and low odor due to the acidic substance disclosed by the applicants in paragraphs 0110 to 0122 of Patent Document 5 (International Publication Patent WO2011 / 049248). It is possible to adopt a method common to the conversion process and the like. In particular, since the co-modified organopolysiloxane can be substantially deodorized, it is solid at 25 ° C., water-soluble, and is an aqueous solution at 25 ° C. when 50 g is dissolved in 1 L of ion-exchanged water. It is preferable to treat with one or more kinds of acidic inorganic salts (preferably sodium hydrogensulfate or the like) characterized by having a pH of 4 or less. For example, as described above (1) Decomposition in which the above acidic inorganic salt is added to a reaction system (for example, a reaction vessel such as a flask) of a co-modified organopolysiloxane composition synthesized by a hydrosilylation reaction and stirred. Treatment, (2) Hydrolysis treatment in which acidic inorganic salt and water or acidic inorganic salt and water and a hydrophilic solvent are added and stirred. The treatment step with the acidic inorganic salt is preferably carried out in the presence of water and / or a hydrophilic medium.
上記の低臭化処理後には、臭気の原因物質である低沸分（プロピオンアルデヒド等）を除去するストリッピング工程を含むことが好ましく、上記の酸性物質による処理および臭気の原因物質のストリッピングは、複数回行うことが好ましい。
After the above-mentioned deodorization treatment, it is preferable to include a stripping step for removing a low boiling point (propionaldehyde, etc.) which is a causative substance of odor, and the treatment with the above-mentioned acidic substance and stripping of the causative substance of odor are carried out. , It is preferable to perform it multiple times.
また、前記酸処理工程後に、特に、得られた共変性オルガノポリシロキサンまたはそれを含む組成物に対して、さらに、100ppm～50000ppmに相当する量のアルカリ性緩衝剤（リン酸ナトリウム，リン酸カリウム，クエン酸ナトリウム，酢酸ナトリウム，炭酸水素ナトリウム等）を添加して中和することが、低臭化の観点から好ましい。
Further, after the acid treatment step, particularly with respect to the obtained co-modified organopolysiloxane or the composition containing the same, an amount of an alkaline buffer (sodium phosphate, potassium phosphate, etc.) corresponding to 100 ppm to 50,000 ppm is further added. It is preferable to neutralize by adding sodium citrate, sodium acetate, sodium hydrogen carbonate, etc. from the viewpoint of low odor.
本発明に係る共変性オルガノポリシロキサンから不要な残滓等を除去する見地から、公知の方法により、ろ過を行ってもよい。
From the viewpoint of removing unnecessary residues and the like from the covariant organopolysiloxane according to the present invention, filtration may be performed by a known method.
〔共変性オルガノポリシロキサンの用途〕
本発明に係る新規な共変性オルガノポリシロキサン（以下、「（Ａ）成分」ともいう）は、疎水性であり、高撥水性を呈するシロキサンデンドロン構造を有するシリルアルキル基と親水性基を同一分子内に有し、かつ低粘度かつ一般に低ＨＬＢであるために、取り扱い性、作業効率、親油性原料と配合安定性に優れるため、各種処理剤および化粧料原料成分として有用であり、特に、化粧料に使用する界面活性剤または表面処理剤、特に粉体の表面処理や粉体の分散に用いられる粉体処理剤または粉体分散剤として極めて有用である。 [Use of covariant organopolysiloxane]
The novel co-modified organopolysiloxane (hereinafter, also referred to as “component (A)”) according to the present invention is hydrophobic and has a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group having the same molecule. Since it has a low viscosity and generally has a low HLB, it is excellent in handleability, work efficiency, lipophilic raw material and compounding stability, and is therefore useful as various treatment agents and cosmetic raw material components. It is extremely useful as a surfactant or surface treatment agent used in a material, particularly as a powder treatment agent or powder dispersant used for surface treatment of powder or dispersion of powder.
本発明に係る新規な共変性オルガノポリシロキサン（以下、「（Ａ）成分」ともいう）は、疎水性であり、高撥水性を呈するシロキサンデンドロン構造を有するシリルアルキル基と親水性基を同一分子内に有し、かつ低粘度かつ一般に低ＨＬＢであるために、取り扱い性、作業効率、親油性原料と配合安定性に優れるため、各種処理剤および化粧料原料成分として有用であり、特に、化粧料に使用する界面活性剤または表面処理剤、特に粉体の表面処理や粉体の分散に用いられる粉体処理剤または粉体分散剤として極めて有用である。 [Use of covariant organopolysiloxane]
The novel co-modified organopolysiloxane (hereinafter, also referred to as “component (A)”) according to the present invention is hydrophobic and has a silylalkyl group having a siloxane dendron structure exhibiting high water repellency and a hydrophilic group having the same molecule. Since it has a low viscosity and generally has a low HLB, it is excellent in handleability, work efficiency, lipophilic raw material and compounding stability, and is therefore useful as various treatment agents and cosmetic raw material components. It is extremely useful as a surfactant or surface treatment agent used in a material, particularly as a powder treatment agent or powder dispersant used for surface treatment of powder or dispersion of powder.
本発明に係る新規な共変性オルガノポリシロキサンの界面活性剤としての使用は、出願人らが上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）の段落０１２４～０１４７に開示した共変性オルガノポリシロキサンの界面活性剤としての使用および各乳化組成物の調製と共通であり、各種乳化組成物の調製の際には、本発明に係る共変性オルガノポリシロキサン(低粘度、好適には低ＨＬＢ)は、特許文献５に開示の共変性オルガノポリシロキサンと併用して乳化することもできる。
The use of the novel co-modified organopolysiloxane according to the present invention as a surfactant is described in paragraphs 0124 to 0147 of Patent Document 5 (International Publication Patent WO2011 / 049248) disclosed by the applicants. Common to the use of polysiloxane as a surfactant and the preparation of each emulsified composition, the co-modified organopolysiloxane (low viscosity, preferably low HLB) according to the present invention is used when preparing various emulsified compositions. ) Can also be emulsified in combination with the co-modified organopolysiloxane disclosed in Patent Document 5.
〔粉体処理剤又は粉体分散剤としての使用〕
本発明に係る共変性オルガノポリシロキサンは、低粘度かつ低ＨＬＢであり、各種粉体の表面に配向して適度な撥水性を付与できるため、化粧料用粉体の表面処理や分散を目的とし、粉体表面処理剤として好適に用いることができる。特に、本発明に係る共変性オルガノポリシロキサンは、公知の共変性オルガノポリシロキサンに比して、粉体処理剤として使用した場合、混合油剤系、特に非シリコーン系の有機油剤における分散安定性が更に良好であり、また、粉体表面を処理剤によって処理して得た粉体組成物を調製したのち、分散媒体となる油剤中にこれを分散させる方法をとった場合でも、従来の粉体処理剤では安定分散が困難であった粉体についても、凝集や沈降、経時的な増粘が起こりにくい安定性に優れた油中粉体分散物を与えることを特徴とする。 [Use as a powder treatment agent or powder dispersant]
The co-modified organopolysiloxane according to the present invention has low viscosity and low HLB, and can be oriented on the surface of various powders to impart appropriate water repellency. Therefore, it is intended for surface treatment and dispersion of cosmetic powders. , Can be suitably used as a powder surface treatment agent. In particular, the co-modified organopolysiloxane according to the present invention has higher dispersion stability in mixed oil-based, especially non-silicone-based organic oil agents, when used as a powder treatment agent, as compared with known co-modified organopolysiloxanes. It is even better, and even when a powder composition obtained by treating the surface of the powder with a treatment agent is prepared and then dispersed in an oil agent as a dispersion medium, the conventional powder is used. Even for powders that were difficult to stably disperse with a treatment agent, it is characterized by providing a powder dispersion in oil having excellent stability, which is less likely to cause aggregation, sedimentation, and thickening over time.
本発明に係る共変性オルガノポリシロキサンは、低粘度かつ低ＨＬＢであり、各種粉体の表面に配向して適度な撥水性を付与できるため、化粧料用粉体の表面処理や分散を目的とし、粉体表面処理剤として好適に用いることができる。特に、本発明に係る共変性オルガノポリシロキサンは、公知の共変性オルガノポリシロキサンに比して、粉体処理剤として使用した場合、混合油剤系、特に非シリコーン系の有機油剤における分散安定性が更に良好であり、また、粉体表面を処理剤によって処理して得た粉体組成物を調製したのち、分散媒体となる油剤中にこれを分散させる方法をとった場合でも、従来の粉体処理剤では安定分散が困難であった粉体についても、凝集や沈降、経時的な増粘が起こりにくい安定性に優れた油中粉体分散物を与えることを特徴とする。 [Use as a powder treatment agent or powder dispersant]
The co-modified organopolysiloxane according to the present invention has low viscosity and low HLB, and can be oriented on the surface of various powders to impart appropriate water repellency. Therefore, it is intended for surface treatment and dispersion of cosmetic powders. , Can be suitably used as a powder surface treatment agent. In particular, the co-modified organopolysiloxane according to the present invention has higher dispersion stability in mixed oil-based, especially non-silicone-based organic oil agents, when used as a powder treatment agent, as compared with known co-modified organopolysiloxanes. It is even better, and even when a powder composition obtained by treating the surface of the powder with a treatment agent is prepared and then dispersed in an oil agent as a dispersion medium, the conventional powder is used. Even for powders that were difficult to stably disperse with a treatment agent, it is characterized by providing a powder dispersion in oil having excellent stability, which is less likely to cause aggregation, sedimentation, and thickening over time.
〔その他の用途〕
本発明に係る新規な共変性オルガノポリシロキサンは、感触改良剤、保湿剤、バインダー、皮膚用の付着・粘着剤（Skin Adhesive）として利用することもできる。また、水と組み合わせることにより皮膜剤、粘度調整剤として利用することもできる。 [Other uses]
The novel co-modified organopolysiloxane according to the present invention can also be used as a feel improver, a moisturizer, a binder, and an adhesive / adhesive for the skin (Skin Adhesive). It can also be used as a film agent and a viscosity adjuster by combining with water.
本発明に係る新規な共変性オルガノポリシロキサンは、感触改良剤、保湿剤、バインダー、皮膚用の付着・粘着剤（Skin Adhesive）として利用することもできる。また、水と組み合わせることにより皮膜剤、粘度調整剤として利用することもできる。 [Other uses]
The novel co-modified organopolysiloxane according to the present invention can also be used as a feel improver, a moisturizer, a binder, and an adhesive / adhesive for the skin (Skin Adhesive). It can also be used as a film agent and a viscosity adjuster by combining with water.
本発明の共変性オルガノポリシロキサンは、化粧料中の親水性及び疎水性の各種の他の成分との馴染みがよく、粉体を含む化粧料中の当該粉体の分散性及び安定性を向上することができる。したがって、本発明の粉体処理剤、並びに、本発明の粉体表面処理剤は、粉体を含む化粧料の安定性、及び、当該粉体の均一分散性を改善することができる。そして、前記粉体表面処理剤で表面処理された粉体を含む化粧料は、安定性が高く、また、当該粉体が化粧料中に均一に分散することを特徴とする。
The co-modified organopolysiloxane of the present invention has good compatibility with various other hydrophilic and hydrophobic components in cosmetics, and improves the dispersibility and stability of the powder in cosmetics containing powder. can do. Therefore, the powder treatment agent of the present invention and the powder surface treatment agent of the present invention can improve the stability of the cosmetic containing the powder and the uniform dispersibility of the powder. The cosmetic containing the powder surface-treated with the powder surface treatment agent is characterized by high stability and the powder being uniformly dispersed in the cosmetic.
本発明の粉体処理剤中の前記共変性オルガノポリシロキサンの配合量は、粉体処理効果を発揮する限り特に限定されるものではないが、例えば、５０～１００重量（質量）％とすることができ、７０～１００質量％が好ましく、９０～１００質量％がより好ましい。
The blending amount of the co-modified organopolysiloxane in the powder treatment agent of the present invention is not particularly limited as long as the powder treatment effect is exhibited, but is, for example, 50 to 100% by weight (mass)%. 70 to 100% by mass is preferable, and 90 to 100% by mass is more preferable.
粉体の表面処理剤として本発明に係る共変性オルガノポリシロキサンを使用する場合、前記共変性オルガノポリシロキサンと粉体又は着色剤の配合量は、粉体又は着色剤１００質量部に対して０．１～３０質量部であることが好ましく、特に０．５～１０質量部の範囲が好適である。前記下限未満では表面処理による効果が十分でない場合があり、処理量が前記上限を超えると、それ以上著しい質感の変化は生じず、粉体と共変性オルガノポリシロキサンの均一な混合物となる傾向が増大する。
When the co-modified organopolysiloxane according to the present invention is used as the surface treatment agent for the powder, the blending amount of the co-modified organopolysiloxane and the powder or the colorant is 0 with respect to 100 parts by mass of the powder or the colorant. .1 to 30 parts by mass is preferable, and the range of 0.5 to 10 parts by mass is particularly preferable. If it is less than the lower limit, the effect of the surface treatment may not be sufficient, and if the treatment amount exceeds the upper limit, no further significant change in texture occurs, and the powder and the covariant organopolysiloxane tend to be a uniform mixture. Increase.
本発明に係る共変性オルガノポリシロキサンは、公知の方法を用いて粉体表面の処理に用いることができる。これらの方法は、特に限定されるものではないが、例えば、以下の方法の中から適宜選択することが可能である。
１．目的の粉体を、処理剤を配合した有機溶剤から選択される媒体中に分散して表面処理する方法。
２．粉体と粉体処理剤を混合したのち、ボールミル、ジェットミルなどの粉砕器を用いて表面処理する方法。
３．処理剤を溶剤に配合し、粉体を分散させて表面に吸着させた後、乾燥して焼結させる処理方法。 The co-modified organopolysiloxane according to the present invention can be used for treating the powder surface by using a known method. These methods are not particularly limited, but can be appropriately selected from the following methods, for example.
1. 1. A method of surface-treating a target powder by dispersing it in a medium selected from an organic solvent containing a treatment agent.
2. 2. A method in which powder and a powder treatment agent are mixed and then surface-treated using a crusher such as a ball mill or jet mill.
3. 3. A treatment method in which a treatment agent is mixed with a solvent, powder is dispersed and adsorbed on the surface, and then dried and sintered.
１．目的の粉体を、処理剤を配合した有機溶剤から選択される媒体中に分散して表面処理する方法。
２．粉体と粉体処理剤を混合したのち、ボールミル、ジェットミルなどの粉砕器を用いて表面処理する方法。
３．処理剤を溶剤に配合し、粉体を分散させて表面に吸着させた後、乾燥して焼結させる処理方法。 The co-modified organopolysiloxane according to the present invention can be used for treating the powder surface by using a known method. These methods are not particularly limited, but can be appropriately selected from the following methods, for example.
1. 1. A method of surface-treating a target powder by dispersing it in a medium selected from an organic solvent containing a treatment agent.
2. 2. A method in which powder and a powder treatment agent are mixed and then surface-treated using a crusher such as a ball mill or jet mill.
3. 3. A treatment method in which a treatment agent is mixed with a solvent, powder is dispersed and adsorbed on the surface, and then dried and sintered.
〔粉体組成物〕
また、本発明は、（Ａ）本発明に係る共変性オルガノポリシロキサンと（Ｂ）粉体又は着色剤を含有してなる粉体組成物に関する。粉体組成物は、上記の方法等により、（Ｂ）粉体又は着色剤と（Ａ）本発明に係る共変性オルガノポリシロキサンを混合することにより得ることができ、粉体の表面処理、粉体の分散性の改善、化粧品原料用プレミックスなどその目的を問わない。 [Powder composition]
The present invention also relates to a powder composition containing (A) a co-modified organopolysiloxane according to the present invention and (B) a powder or a colorant. The powder composition can be obtained by mixing (B) a powder or a colorant with (A) the co-modified organopolysiloxane according to the present invention by the above method or the like, and the surface treatment of the powder and the powder can be obtained. Regardless of the purpose, such as improving the dispersibility of the body and premixing for cosmetic ingredients.
また、本発明は、（Ａ）本発明に係る共変性オルガノポリシロキサンと（Ｂ）粉体又は着色剤を含有してなる粉体組成物に関する。粉体組成物は、上記の方法等により、（Ｂ）粉体又は着色剤と（Ａ）本発明に係る共変性オルガノポリシロキサンを混合することにより得ることができ、粉体の表面処理、粉体の分散性の改善、化粧品原料用プレミックスなどその目的を問わない。 [Powder composition]
The present invention also relates to a powder composition containing (A) a co-modified organopolysiloxane according to the present invention and (B) a powder or a colorant. The powder composition can be obtained by mixing (B) a powder or a colorant with (A) the co-modified organopolysiloxane according to the present invention by the above method or the like, and the surface treatment of the powder and the powder can be obtained. Regardless of the purpose, such as improving the dispersibility of the body and premixing for cosmetic ingredients.
〔油中粉体分散物〕
また、本発明でいう油中粉体分散物とは、上記の様にして得た粉体組成物を油剤中に分散したもの、或いは油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加して混合分散したものを意味し、その形態は液状分散物である。かかる液状分散物は「スラリー」と呼ぶことがある。特に、本発明に係る共変性オルガノポリシロキサンは、上記の特許文献５に開示された共変性オルガノポリシロキサンと同一条件では、十分な処理ができないような酸化亜鉛等の無機粉体であっても、低粘度のスラリーを調製できる点で有用である。 [Powder dispersion in oil]
Further, the powder dispersion in oil referred to in the present invention is a powder composition obtained as described above dispersed in an oil agent, or a co-modified organopolysiloxane dissolved or dispersed in the oil agent. It means a product in which powder is added and mixed and dispersed, and the form thereof is a liquid dispersion. Such a liquid dispersion may be referred to as a "slurry". In particular, the co-modified organopolysiloxane according to the present invention may be an inorganic powder such as zinc oxide that cannot be sufficiently treated under the same conditions as the co-modified organopolysiloxane disclosed in Patent Document 5 above. It is useful in that a low-viscosity slurry can be prepared.
また、本発明でいう油中粉体分散物とは、上記の様にして得た粉体組成物を油剤中に分散したもの、或いは油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加して混合分散したものを意味し、その形態は液状分散物である。かかる液状分散物は「スラリー」と呼ぶことがある。特に、本発明に係る共変性オルガノポリシロキサンは、上記の特許文献５に開示された共変性オルガノポリシロキサンと同一条件では、十分な処理ができないような酸化亜鉛等の無機粉体であっても、低粘度のスラリーを調製できる点で有用である。 [Powder dispersion in oil]
Further, the powder dispersion in oil referred to in the present invention is a powder composition obtained as described above dispersed in an oil agent, or a co-modified organopolysiloxane dissolved or dispersed in the oil agent. It means a product in which powder is added and mixed and dispersed, and the form thereof is a liquid dispersion. Such a liquid dispersion may be referred to as a "slurry". In particular, the co-modified organopolysiloxane according to the present invention may be an inorganic powder such as zinc oxide that cannot be sufficiently treated under the same conditions as the co-modified organopolysiloxane disclosed in Patent Document 5 above. It is useful in that a low-viscosity slurry can be prepared.
上記油剤は、液状分散物を調製可能であれば特に限定されるものではなく、化粧料の成分として一般に使用されるものであり、通常は室温で液体であるが、ワックスのような固形であってもよく、後述する高粘度かつ粘稠なガム状或いはペースト状であってもよい。かかる油剤は、（Ｃ）５～１００℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される１以上の油剤が好適である。特に、（Ｃ１）５～１００℃で液状であるシリコーンオイルおよび（Ｃ２）炭化水素油および脂肪酸エステル油から選ばれる1種類以上を含む油剤の使用が好ましい。
The above-mentioned oil agent is not particularly limited as long as a liquid dispersion can be prepared, and is generally used as a component of cosmetics. It is usually liquid at room temperature, but is a solid such as wax. It may be in the form of a highly viscous and viscous gum or paste, which will be described later. As such an oil agent, one or more oil agents selected from (C) silicone oil, which is liquid at 5 to 100 ° C., a non-polar organic compound, or a low-polar organic compound, are suitable. In particular, it is preferable to use an oil containing one or more selected from (C1) silicone oil which is liquid at 5 to 100 ° C. and (C2) hydrocarbon oil and fatty acid ester oil.
本発明の油中分散物は、たとえば下記の方法のような公知の方法によって適宜調製することが可能である。
１．前記の如くして得た粉体組成物を、エステル油やシリコーン油等の油剤中に添加して分散する方法。
２．上記の油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加してボールミル、ビーズミル、サンドミル等の分散機器で混合する方法。
そして、得られた油中粉体分散物は、そのまま外用剤組成物（特に、化粧料）に配合することができる。 The dispersion in oil of the present invention can be appropriately prepared by a known method such as the following method.
1. 1. A method of adding and dispersing the powder composition obtained as described above in an oil agent such as ester oil or silicone oil.
2. 2. A method in which a covariant organopolysiloxane is dissolved or dispersed in the above oil, powder is added thereto, and the mixture is mixed with a dispersion device such as a ball mill, a bead mill, or a sand mill.
Then, the obtained powder dispersion in oil can be directly blended into the external preparation composition (particularly, cosmetics).
１．前記の如くして得た粉体組成物を、エステル油やシリコーン油等の油剤中に添加して分散する方法。
２．上記の油剤中に共変性オルガノポリシロキサンを溶解または分散し、これに粉体を添加してボールミル、ビーズミル、サンドミル等の分散機器で混合する方法。
そして、得られた油中粉体分散物は、そのまま外用剤組成物（特に、化粧料）に配合することができる。 The dispersion in oil of the present invention can be appropriately prepared by a known method such as the following method.
1. 1. A method of adding and dispersing the powder composition obtained as described above in an oil agent such as ester oil or silicone oil.
2. 2. A method in which a covariant organopolysiloxane is dissolved or dispersed in the above oil, powder is added thereto, and the mixture is mixed with a dispersion device such as a ball mill, a bead mill, or a sand mill.
Then, the obtained powder dispersion in oil can be directly blended into the external preparation composition (particularly, cosmetics).
本発明に係る共変性オルガノポリシロキサンを含有する粉体組成物および油中分散物は、外用剤組成物や、特に化粧料または化粧料原料として好適に使用することができる。
The powder composition and the dispersion in oil containing the co-modified organopolysiloxane according to the present invention can be suitably used as an external preparation composition, particularly as a cosmetic or a cosmetic raw material.
〔（Ｂ）粉体又は着色剤〕
本発明に係る粉体組成物および油中粉体分散物等に用いる、（Ｂ）粉体又は着色剤は、化粧料の成分として一般に使用されるものであり、白色及び着色顔料、並びに、体質顔料を含む。白色及び着色顔料は化粧料の着色等に使用され、一方、体質顔料は、化粧料の感触改良等に使用される。本発明における「粉体」としては、化粧料に通常使用される白色及び着色顔料、並びに、体質顔料を特に制限なく使用することができる。本発明において、１種類又は２種類以上の粉体を配合することが好ましい。粉体の形状（球状、棒状、針状、板状、不定形状、紡錘状、繭状等）、粒子径（煙霧状、微粒子、顔料級等）、及び、粒子構造（多孔質、無孔質等）は何ら限定されるものではないが、平均一次粒子径が１ｎｍ～１００μｍの範囲にあることが好ましい。特に、これらの粉体又は着色剤を顔料として配合する場合、平均粒子径が１ｎｍ～２０μｍの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体から選択される１種類又は２種類以上を配合することが好ましい。 [(B) Powder or colorant]
The (B) powder or colorant used in the powder composition and the powder dispersion in oil according to the present invention is generally used as a component of cosmetics, and is a white and colored pigment, and a constitution. Contains pigments. White and colored pigments are used for coloring cosmetics and the like, while extender pigments are used for improving the feel of cosmetics and the like. As the "powder" in the present invention, white and colored pigments usually used in cosmetics and extender pigments can be used without particular limitation. In the present invention, it is preferable to mix one kind or two or more kinds of powders. Powder shape (spherical, rod-shaped, needle-shaped, plate-shaped, indefinite shape, spindle-shaped, cocoon-shaped, etc.), particle size (fumes, fine particles, pigment grade, etc.), and particle structure (porous, non-porous, etc.) Etc.) is not limited in any way, but it is preferable that the average primary particle size is in the range of 1 nm to 100 μm. In particular, when these powders or colorants are blended as pigments, one or more selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle size in the range of 1 nm to 20 μm. Is preferably blended.
本発明に係る粉体組成物および油中粉体分散物等に用いる、（Ｂ）粉体又は着色剤は、化粧料の成分として一般に使用されるものであり、白色及び着色顔料、並びに、体質顔料を含む。白色及び着色顔料は化粧料の着色等に使用され、一方、体質顔料は、化粧料の感触改良等に使用される。本発明における「粉体」としては、化粧料に通常使用される白色及び着色顔料、並びに、体質顔料を特に制限なく使用することができる。本発明において、１種類又は２種類以上の粉体を配合することが好ましい。粉体の形状（球状、棒状、針状、板状、不定形状、紡錘状、繭状等）、粒子径（煙霧状、微粒子、顔料級等）、及び、粒子構造（多孔質、無孔質等）は何ら限定されるものではないが、平均一次粒子径が１ｎｍ～１００μｍの範囲にあることが好ましい。特に、これらの粉体又は着色剤を顔料として配合する場合、平均粒子径が１ｎｍ～２０μｍの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体から選択される１種類又は２種類以上を配合することが好ましい。 [(B) Powder or colorant]
The (B) powder or colorant used in the powder composition and the powder dispersion in oil according to the present invention is generally used as a component of cosmetics, and is a white and colored pigment, and a constitution. Contains pigments. White and colored pigments are used for coloring cosmetics and the like, while extender pigments are used for improving the feel of cosmetics and the like. As the "powder" in the present invention, white and colored pigments usually used in cosmetics and extender pigments can be used without particular limitation. In the present invention, it is preferable to mix one kind or two or more kinds of powders. Powder shape (spherical, rod-shaped, needle-shaped, plate-shaped, indefinite shape, spindle-shaped, cocoon-shaped, etc.), particle size (fumes, fine particles, pigment grade, etc.), and particle structure (porous, non-porous, etc.) Etc.) is not limited in any way, but it is preferable that the average primary particle size is in the range of 1 nm to 100 μm. In particular, when these powders or colorants are blended as pigments, one or more selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle size in the range of 1 nm to 20 μm. Is preferably blended.
粉体としては、例えば、無機粉体、有機粉体、界面活性剤金属塩粉体（金属石鹸）、有色顔料、パール顔料、金属粉末顔料等が挙げられ、これらを複合化したものを使用することができる。さらに、これらの表面に撥水化処理を行ったものを挙げることができる。
Examples of the powder include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment and the like, and a composite of these is used. be able to. Further, those having a water-repellent treatment on these surfaces can be mentioned.
これらの具体例は、出願人らが上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）の段落０１５０～０１５２に開示した粉体又は着色剤と共通である。本発明において使用する粉体としては、酸化チタン、酸化亜鉛、酸化鉄、酸化セリウム及びこれらの複合体等の紫外線吸収・散乱能を有する無機粉体が好ましく、特に、表面に撥水化処理を行ったものが特に好ましい。上記複合体は、表面処理粉体、無機粉体内部に他の無機粒子が分散した粉体などを指すものである。
These specific examples are common to the powder or colorant disclosed by the applicants in paragraphs 0150 to 0152 of Patent Document 5 (International Publication Patent WO2011 / 049248). As the powder used in the present invention, an inorganic powder having an ultraviolet absorbing / scattering ability such as titanium oxide, zinc oxide, iron oxide, cerium oxide and a composite thereof is preferable, and the surface thereof is particularly treated with a water repellent treatment. The one that has been done is particularly preferable. The composite refers to a surface-treated powder, a powder in which other inorganic particles are dispersed inside the inorganic powder, and the like.
（Ａ）前記共変性オルガノポリシロキサンと（Ｂ）粉体または着色剤の混合物は共変性オルガノポリシロキサン中に粉体が分散した形態であり、当該混合物における粉体の配合量は、特に限定されるものではないが、混合物全体の５０～９９質量％の範囲が好適であり、８０～９０質量％がより好適である。
The mixture of (A) the co-modified organopolysiloxane and (B) the powder or the colorant has a form in which the powder is dispersed in the co-modified organopolysiloxane, and the blending amount of the powder in the mixture is particularly limited. Although not, the range of 50 to 99% by mass of the whole mixture is preferable, and 80 to 90% by mass is more preferable.
〔（Ｃ）油剤〕
本発明に係る油中粉体分散物等に用いる油剤は、好適には、（Ｃ）５～１００℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される１以上の油剤であり、非極性有機化合物及び低極性有機化合物としては、炭化水素油及び脂肪酸エステル油が好ましい。 [(C) Oil agent]
The oil agent used for the powder dispersion in oil according to the present invention is preferably one or more selected from (C) silicone oil, non-polar organic compound or low-polar organic compound which is liquid at 5 to 100 ° C. As the oil agent, the non-polar organic compound and the low-polar organic compound are preferably hydrocarbon oil and fatty acid ester oil.
本発明に係る油中粉体分散物等に用いる油剤は、好適には、（Ｃ）５～１００℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される１以上の油剤であり、非極性有機化合物及び低極性有機化合物としては、炭化水素油及び脂肪酸エステル油が好ましい。 [(C) Oil agent]
The oil agent used for the powder dispersion in oil according to the present invention is preferably one or more selected from (C) silicone oil, non-polar organic compound or low-polar organic compound which is liquid at 5 to 100 ° C. As the oil agent, the non-polar organic compound and the low-polar organic compound are preferably hydrocarbon oil and fatty acid ester oil.
特に、本発明に係る共変性オルガノポリシロキサンは、（Ｃ１）５～１００℃で液状であるシリコーンオイルだけでなく、（Ｃ２）炭化水素油および脂肪酸エステル油から選ばれる1種類以上を含む油剤に対して優れた親和性を有し、安定した油中粉体分散物（スラリー等）を形成できるため、成分（Ｃ１）である油剤と成分（Ｃ２）である油剤の混合系油剤、あるいは、これらを共に含む化粧料原料および外用剤組成物として極めて有用である。
In particular, the co-modified organopolysiloxane according to the present invention is an oil agent containing not only (C1) a silicone oil liquid at 5 to 100 ° C. but also (C2) one or more selected from hydrocarbon oils and fatty acid ester oils. Since it has an excellent affinity for the oil and can form a stable powder dispersion (slurry, etc.) in oil, it is a mixed oil agent of an oil agent as a component (C1) and an oil agent as a component (C2), or these. It is extremely useful as a cosmetic raw material and an external preparation composition containing both of them.
油剤には、公知の植物性油脂類、動物性油脂類、高級アルコール類、液状脂肪酸トリグリセライド、人工皮脂、フッ素系油から選択される１種類または２種類以上を併用しても良い。前記共変性オルガノポリシロキサンはこれらの非シリコーン系油剤に対しても優れた分散性を示すので、炭化水素油及び脂肪酸エステル油を安定に化粧料に配合でき、これらの非シリコーン系油剤による保湿特性を維持することができる。したがって、前記共変性オルガノポリシロキサンは、これらの非シリコーン系油剤の化粧料中における経時安定性を改善することができる。
As the oil agent, one kind or two or more kinds selected from known vegetable fats and oils, animal fats and oils, higher alcohols, liquid fatty acid triglyceride, artificial sebum, and fluorine-based oil may be used in combination. Since the co-modified organopolysiloxane exhibits excellent dispersibility even with respect to these non-silicone oils, hydrocarbon oils and fatty acid ester oils can be stably blended into cosmetics, and the moisturizing properties of these non-silicone oils. Can be maintained. Therefore, the covariant organopolysiloxane can improve the stability of these non-silicone oils over time in cosmetics.
また、炭化水素油及び／又は脂肪酸エステル油をシリコーンオイルと併用することにより、シリコーンオイル特有のさっぱりとした感触に加えて、肌上の水分を保持し、化粧料に肌や毛髪が潤うような保湿感（「しっとりした感触」ともいう）や滑らかな感触を付与することができ、しかも、化粧料の経時安定性を損なわないという利点がある。更に、炭化水素油及び／又は脂肪酸エステル油とシリコーンオイルを含有する化粧料は、これらの保湿成分（炭化水素油及び／又は脂肪酸エステル油）を肌上又は毛髪上により安定かつ均一な状態で塗布することができるので、保湿成分の肌上の保湿効果が向上する。したがって、非シリコーン系油剤（炭化水素油、脂肪酸エステル油等）のみを含む化粧料に比して、非シリコーン系油剤と共にシリコーンオイルを含む化粧料は、より滑らかでしっとりした感触を付与することができるという利点がある。
In addition, by using hydrocarbon oil and / or fatty acid ester oil in combination with silicone oil, in addition to the refreshing feel peculiar to silicone oil, it retains moisture on the skin and moisturizes the skin and hair with cosmetics. It has the advantages of being able to impart a moisturizing feeling (also referred to as "moist feeling") and a smooth feeling, and not impairing the stability of the cosmetics over time. Further, for cosmetics containing hydrocarbon oil and / or fatty acid ester oil and silicone oil, these moisturizing components (hydrogen hydrocarbon oil and / or fatty acid ester oil) are applied on the skin or hair in a more stable and uniform state. Therefore, the moisturizing effect of the moisturizing ingredient on the skin is improved. Therefore, a cosmetic containing a silicone oil together with a non-silicone oil may give a smoother and moist feel than a cosmetic containing only a non-silicone oil (hydrocarbon oil, fatty acid ester oil, etc.). There is an advantage that it can be done.
これらの油剤は、出願人らが上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）の段落０１３０～０１３５、段落０２０６等に開示したものと共通である。なお、フッ素系油としては、パーフルオロポリエーテル、パーフルオロデカリン、パーフルオロオクタン等が挙げられる。
These oils are the same as those disclosed by the applicants in paragraphs 0130 to 0135, paragraph 0206, etc. of Patent Document 5 (International Publication Patent WO2011 / 049248). Examples of the fluorine-based oil include perfluoropolyether, perfluorodecalin, and perfluorooctane.
本発明の油中粉体分散物中の油剤の配合量は特に限定されるものではないが、化粧料用原料中の０．１～５０質量％の範囲内で配合することが好ましく、０．５～２５質量％がより好ましい。
The blending amount of the oil agent in the powder dispersion in oil of the present invention is not particularly limited, but it is preferably blended in the range of 0.1 to 50% by mass in the raw material for cosmetics, and 0. 5 to 25% by mass is more preferable.
前記共変性オルガノポリシロキサン、それを含有してなる粉体組成物または油中粉体分散物は、外用剤組成物や、特に化粧料または化粧料原料として好適に使用することができ、これらの外用剤組成物、特に化粧料または医薬である外用剤組成物は、本願発明に包含される。
The co-modified organopolysiloxane, a powder composition containing the same, or a powder dispersion in oil can be suitably used as an external preparation composition, particularly as a cosmetic or a raw material for cosmetics, and these External preparation compositions, particularly cosmetic or pharmaceutical external preparation compositions, are included in the present invention.
特に、前記共変性オルガノポリシロキサン、それを含有してなる粉体組成物または油中粉体分散物は、メークアップ化粧料原料として好適であり、これらを含有してなる外用剤組成物（化粧料および医薬の形態を含む）、特に各種メークアップ化粧料は、本願発明の特に好適な形態に包含される。
In particular, the co-modified organopolysiloxane, a powder composition containing the same, or a powder dispersion in oil is suitable as a raw material for make-up cosmetics, and an external preparation composition (makeup) containing these is suitable. (Including food and pharmaceutical forms), in particular various make-up cosmetics, are included in the particularly preferred forms of the present invention.
本発明の化粧料には、更に、（Ｄ）水、エタノール等のアルコール（プレミックスとしての利用を含む）、（Ｅ）その他の界面活性剤、（Ｆ）多価アルコール及び／又は低級一価アルコール、（Ｇ）無機塩類及び／又は有機酸塩、（Ｈ）架橋性オルガノポリシロキサン、オルガノポリシロキサンエラストマー球状粉体、シリコーン樹脂、アクリルシリコーンデンドリマーコポリマー、シリコーン生ゴム、ポリアミド変性シリコーン、アルキル変性シリコーンワックス、アルキル変性シリコーンレジンワックス、シリコーンポリエーテルエラストマーゲル、PITUITOUS SILICONE FLUIDS 、液状かつ微架橋性のオルガノポリシロキサン等の成分（Ａ）以外のシリコーン成分、（Ｊ）水溶性高分子、（Ｋ）紫外線防御成分（無機系と有機系の紫外線防御成分／ＵＶ－Ａに対応した紫外線防御成分とＵＶ－Ｂに対応した紫外線防御成分との併用を含む）を配合することができ、これらは、上記の特許文献７（特開２０１３－１５１６５７号公報）の段落０１０１～０１１３に開示したものと共通である。
The cosmetics of the present invention further include (D) water, alcohols such as ethanol (including use as a premix), (E) other surfactants, (F) polyhydric alcohols and / or lower monovalents. Alcohol, (G) inorganic salts and / or organic acid salts, (H) crosslinkable organopolysiloxane, organopolysiloxane elastomer spherical powder, silicone resin, acrylic silicone dendrimer copolymer, silicone raw rubber, polyamide-modified silicone, alkyl-modified silicone wax , Alkyl-modified silicone resin wax, Silicone polyether elastomer gel, PITUITOUS SILICONE FLUIDS, Liquid and micro-crosslinkable organopolysiloxane, etc. Silicone components other than (A), (J) Water-soluble polymer, (K) UV protection Ingredients (including a combination of an inorganic and organic UV protection component / UV-A compatible UV protection component and a UV-B compatible UV protection component) can be blended, and these can be blended with the above patents. It is the same as that disclosed in paragraphs 0101 to 0113 of Document 7 (Japanese Unexamined Patent Publication No. 2013-151657).
本発明の化粧料には、上記の各成分の他に、油溶性ゲル化剤、有機変性粘土鉱物、防菌防腐剤、生理活性成分、美肌用成分、ｐＨ調整剤、酸化防止剤、溶媒、キレート剤、保湿成分、香料、デオドラント剤等の各種成分を、本発明の目的を損なわない範囲で使用することができる。これらの化粧品用任意成分は、出願人らが上記の特許文献７（特開２０１３－１５１６５７号公報）に開示したものと共通である。
In addition to the above components, the cosmetic of the present invention includes oil-soluble gelling agents, organically modified clay minerals, antibacterial preservatives, bioactive ingredients, skin-beautifying ingredients, pH regulators, antioxidants, solvents, etc. Various components such as a chelating agent, a moisturizing component, a fragrance, and a deodorant can be used as long as the object of the present invention is not impaired. These optional cosmetic ingredients are the same as those disclosed by the applicants in Patent Document 7 (Japanese Unexamined Patent Publication No. 2013-151657).
本発明に係る外用剤組成物は、化粧料または医薬として人体に適用される組成物であれば、特にその制限はない。本発明の化粧料は、具体的な製品としては、皮膚洗浄剤製品、スキンケア製品、メークアップ製品、制汗剤製品、紫外線防御製品などの皮膚用化粧品；毛髪用洗浄剤製品、整髪料製品、毛髪用着色料製品、養毛料製品、ヘアリンス製品、ヘアコンディショナー製品、ヘアトリートメント製品等の頭髪用化粧品；浴用化粧品が例示される。本発明の医薬は、発毛剤、育毛剤、鎮痛剤、殺菌剤、抗炎症剤、清涼剤、皮膚老化防止剤が例示されるが、これらに限定されない。
The external preparation composition according to the present invention is not particularly limited as long as it is a composition applied to the human body as a cosmetic or a pharmaceutical. Specific products of the present invention include skin cosmetics such as skin cleaning products, skin care products, makeup products, antiperspirant products, and UV protection products; hair cleaning products, hair styling products, etc. Hair cosmetics such as hair coloring products, hair nourishing products, hair rinsing products, hair conditioner products, and hair treatment products; bath cosmetics are exemplified. Examples of the pharmaceutical of the present invention include, but are not limited to, hair growth agents, hair growth agents, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and skin antiaging agents.
本発明に係る外用剤組成物の種類、形態および容器は、出願人らが上記の特許文献５（国際公開特許 ＷＯ２０１１／０４９２４８号公報）の段落０２３０～０２３３等に開示したものと共通であるが、前記共変性オルガノポリシロキサンは、特に、各種メークアップ化粧料の原料として有用であり、本発明に係る化粧料は、（Ａ）前記の共変性オルガノポリシロキサン、（Ｂ）粉体又は着色剤 、（Ｃ１）５～１００℃で液状であるシリコーンオイル並びに（Ｃ２）炭化水素油および脂肪酸エステル油から選ばれる1種類以上を含む油剤を含有してなるメークアップ化粧料が最も好適である。
The type, form and container of the external preparation composition according to the present invention are the same as those disclosed by the applicants in paragraphs 0230 to 0233 of Patent Document 5 (International Publication Patent WO2011 / 049248). The co-modified organopolysiloxane is particularly useful as a raw material for various make-up cosmetics, and the cosmetic according to the present invention is (A) the co-modified organopolysiloxane, (B) a powder or a colorant. , (C1) A make-up cosmetic containing a silicone oil liquid at 5 to 100 ° C. and (C2) an oil containing at least one selected from a hydrocarbon oil and a fatty acid ester oil is most suitable.
以下、実施例および比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。粘度（動粘度）は２５℃における測定値である。なお、下記組成式において、Ｍｅ３ＳｉＯ基（または、Ｍｅ３Ｓｉ基）を「Ｍ」、Ｍｅ２ＳｉＯ基を「Ｄ」、ＭｅＨＳｉＯ基を「ＤＨ」と表記し、Ｄ中のメチル基をいずれかの置換基（Ｒ）によって変性した単位をＤＲと表記する。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Viscosity (kinematic viscosity) is a measured value at 25 ° C. In the following composition formula, the Me3SiO group (or Me3Si group) is referred to as "M", the Me2SiO group is referred to as "D", the MeHSiO group is referred to as " DH ", and the methyl group in D is represented by any of the substituents (D). The unit denatured by R ) is referred to as DR.
（実施例１）
＜共変性オルガノポリシロキサン化合物Ｐ１の合成＞
反応器に平均組成式 ＭＤ５．２ＤＨ ８．０Ｍ で表されるメチルハイドロジェンポリシロキサン３１．４３ｇ、トリストリメチルシロキシビニルシラン３２．１７ｇ、ヘキサデセン２７．１１ｇ、ジグリセリンモノアリルエーテル９．２８ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ５．２ＤＲ１ ３．２ＤＲ２ １．３ＤＲ３ ３．５Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。
式中、Ｒ１、Ｒ２およびＲ３は下記に示した構造である。
Ｒ１＝ －Ｃ２Ｈ４Ｓｉ（ＯＳｉＭｅ３）３
Ｒ２＝ －Ｃ３Ｈ６Ｏ－－Ｘで表される親水基であり、Ｘはジグリセリン部分
Ｒ３＝ －Ｃ１６Ｈ３３
この生成物は、淡褐色の粘性半透明液体であった。 (Example 1)
<Synthesis of covariant organopolysiloxane compound P1>
Methylhydrogenpolysiloxane 31.43 g, tristrimethylsiloxyvinylsilane 32.17 g, hexadecene 27.11 g, diglycerin monoallyl ether 9.28 g represented by the average composition formula MD 5.2 DH 8.0 M in the reactor. Was charged and heated to 65 ° C. with stirring under nitrogen flow. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). After that, it was subjected to filtration treatment to obtain a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 5.2 DR1 3.2 DR2 1.3 DR3 3.5 M. ..
In the formula, R 1 , R 2 and R 3 have the structures shown below.
R 1 = -C 2 H 4 Si (OSiMe 3 ) 3
R 2 = -C 3 H 6 is a hydrophilic group represented by O-X, where X is the diglycerin moiety R 3 = -C 16 H 33 .
The product was a light brown viscous translucent liquid.
＜共変性オルガノポリシロキサン化合物Ｐ１の合成＞
反応器に平均組成式 ＭＤ５．２ＤＨ ８．０Ｍ で表されるメチルハイドロジェンポリシロキサン３１．４３ｇ、トリストリメチルシロキシビニルシラン３２．１７ｇ、ヘキサデセン２７．１１ｇ、ジグリセリンモノアリルエーテル９．２８ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ５．２ＤＲ１ ３．２ＤＲ２ １．３ＤＲ３ ３．５Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。
式中、Ｒ１、Ｒ２およびＲ３は下記に示した構造である。
Ｒ１＝ －Ｃ２Ｈ４Ｓｉ（ＯＳｉＭｅ３）３
Ｒ２＝ －Ｃ３Ｈ６Ｏ－－Ｘで表される親水基であり、Ｘはジグリセリン部分
Ｒ３＝ －Ｃ１６Ｈ３３
この生成物は、淡褐色の粘性半透明液体であった。 (Example 1)
<Synthesis of covariant organopolysiloxane compound P1>
Methylhydrogenpolysiloxane 31.43 g, tristrimethylsiloxyvinylsilane 32.17 g, hexadecene 27.11 g, diglycerin monoallyl ether 9.28 g represented by the average composition formula MD 5.2 DH 8.0 M in the reactor. Was charged and heated to 65 ° C. with stirring under nitrogen flow. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). After that, it was subjected to filtration treatment to obtain a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 5.2 DR1 3.2 DR2 1.3 DR3 3.5 M. ..
In the formula, R 1 , R 2 and R 3 have the structures shown below.
R 1 = -C 2 H 4 Si (OSiMe 3 ) 3
R 2 = -C 3 H 6 is a hydrophilic group represented by O-X, where X is the diglycerin moiety R 3 = -C 16 H 33 .
The product was a light brown viscous translucent liquid.
（実施例２）
＜共変性オルガノポリシロキサン化合物Ｐ２の合成＞
反応器に平均組成式 ＭＤ５．２ＤＨ ８．０Ｍ で表されるメチルハイドロジェンポリシロキサン３１．６２ｇ、トリストリメチルシロキシビニルシラン３０．３４ｇ、ヘキサデセン２７．２７ｇ、ジグリセリンモノアリルエーテル１０．７７ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ５．２ＤＲ１ ３．０ＤＲ２ １．５ＤＲ３ ３．５Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 2)
<Synthesis of covariant organopolysiloxane compound P2>
Methylhydrogenpolysiloxane 31.62 g, tristrimethylsiloxyvinylsilane 30.34 g, hexadecene 27.27 g, diglycerin monoallyl ether 10.77 g represented by the average composition formula MD 5.2 DH 8.0 M in the reactor. Was charged and heated to 65 ° C. with stirring under nitrogen flow. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). After that, it was subjected to filtration treatment to obtain a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 5.2 DR1 3.0 DR2 1.5 DR3 3.5 M. .. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
＜共変性オルガノポリシロキサン化合物Ｐ２の合成＞
反応器に平均組成式 ＭＤ５．２ＤＨ ８．０Ｍ で表されるメチルハイドロジェンポリシロキサン３１．６２ｇ、トリストリメチルシロキシビニルシラン３０．３４ｇ、ヘキサデセン２７．２７ｇ、ジグリセリンモノアリルエーテル１０．７７ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ５．２ＤＲ１ ３．０ＤＲ２ １．５ＤＲ３ ３．５Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 2)
<Synthesis of covariant organopolysiloxane compound P2>
Methylhydrogenpolysiloxane 31.62 g, tristrimethylsiloxyvinylsilane 30.34 g, hexadecene 27.27 g, diglycerin monoallyl ether 10.77 g represented by the average composition formula MD 5.2 DH 8.0 M in the reactor. Was charged and heated to 65 ° C. with stirring under nitrogen flow. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). After that, it was subjected to filtration treatment to obtain a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 5.2 DR1 3.0 DR2 1.5 DR3 3.5 M. .. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
（実施例３）
＜共変性オルガノポリシロキサン化合物Ｐ３の合成＞
反応器に平均組成式 ＭＤ１８ＤＨ ３．４Ｍ で表されるメチルハイドロジェンポリシロキサン６５．６６ｇ、トリストリメチルシロキシビニルシラン２．２７ｇ、ヘキサデセン２５．７２ｇ、ジグリセリンモノアリルエーテル６．３５ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ１８ＤＲ１ ０．２ＤＲ２ ０．７ＤＲ３ ２．６Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 3)
<Synthesis of covariant organopolysiloxane compound P3>
The reactor was charged with 65.66 g of methylhydrogenpolysiloxane represented by the average composition formula MD 18 DH 3.4 M, 2.27 g of tristrimethylsiloxyvinylsilane, 25.72 g of hexadecene, and 6.35 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 18 DR1 0.2 DR2 0.7 DR3 2.6 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
＜共変性オルガノポリシロキサン化合物Ｐ３の合成＞
反応器に平均組成式 ＭＤ１８ＤＨ ３．４Ｍ で表されるメチルハイドロジェンポリシロキサン６５．６６ｇ、トリストリメチルシロキシビニルシラン２．２７ｇ、ヘキサデセン２５．７２ｇ、ジグリセリンモノアリルエーテル６．３５ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ１８ＤＲ１ ０．２ＤＲ２ ０．７ＤＲ３ ２．６Ｍ で表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 3)
<Synthesis of covariant organopolysiloxane compound P3>
The reactor was charged with 65.66 g of methylhydrogenpolysiloxane represented by the average composition formula MD 18 DH 3.4 M, 2.27 g of tristrimethylsiloxyvinylsilane, 25.72 g of hexadecene, and 6.35 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 18 DR1 0.2 DR2 0.7 DR3 2.6 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
（実施例４）
＜共変性オルガノポリシロキサン化合物Ｐ４の合成＞
反応器に平均組成式 ＭＤ２９ＤＨ ７．３Ｍ で表されるメチルハイドロジェンポリシロキサン５７．７８ｇ、トリストリメチルシロキシビニルシラン１１．２５ｇ、ヘキサデセン２７．４３ｇ、ジグリセリンモノアリルエーテル３．５４ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ２９ＤＲ１ １．６ＤＲ２ ０．７ＤＲ３ ５．０Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 4)
<Synthesis of covariant organopolysiloxane compound P4>
The reactor was charged with 57.78 g of methylhydrogenpolysiloxane represented by the average composition formula MD 29 DH 7.3 M, 11.25 g of tristrimethylsiloxyvinylsilane, 27.43 g of hexadecene, and 3.54 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 29 DR1 1.6 DR2 0.7 DR3 5.0 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
＜共変性オルガノポリシロキサン化合物Ｐ４の合成＞
反応器に平均組成式 ＭＤ２９ＤＨ ７．３Ｍ で表されるメチルハイドロジェンポリシロキサン５７．７８ｇ、トリストリメチルシロキシビニルシラン１１．２５ｇ、ヘキサデセン２７．４３ｇ、ジグリセリンモノアリルエーテル３．５４ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ２９ＤＲ１ １．６ＤＲ２ ０．７ＤＲ３ ５．０Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Example 4)
<Synthesis of covariant organopolysiloxane compound P4>
The reactor was charged with 57.78 g of methylhydrogenpolysiloxane represented by the average composition formula MD 29 DH 7.3 M, 11.25 g of tristrimethylsiloxyvinylsilane, 27.43 g of hexadecene, and 3.54 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 29 DR1 1.6 DR2 0.7 DR3 5.0 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
（比較例１）
＜共変性オルガノポリシロキサン化合物Ｒ１の合成＞
反応器に平均組成式ＭＤ１５ＤＨ ３．０Ｍで表されるメチルハイドロジェンポリシロキサン６１．２６ｇ、トリストリメチルシロキシビニルシラン３２．３２ｇ、ジグリセリンモノアリルエーテル６．４２ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ１６ＤＲ１ ２．４ＤＲ２ ０．６Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Comparative Example 1)
<Synthesis of covariant organopolysiloxane compound R1>
A reactor was charged with 61.26 g of methylhydrogenpolysiloxane represented by the average composition formula MD 15 DH 3.0 M, 32.32 g of tristrimethylsiloxyvinylsilane, and 6.42 g of diglycerin monoallyl ether under nitrogen flow. The mixture was heated to 65 ° C. with stirring. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 16 DR1 2.4 DR2 0.6 M was obtained. In the formula, R 1 and R 2 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
＜共変性オルガノポリシロキサン化合物Ｒ１の合成＞
反応器に平均組成式ＭＤ１５ＤＨ ３．０Ｍで表されるメチルハイドロジェンポリシロキサン６１．２６ｇ、トリストリメチルシロキシビニルシラン３２．３２ｇ、ジグリセリンモノアリルエーテル６．４２ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ１６ＤＲ１ ２．４ＤＲ２ ０．６Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Comparative Example 1)
<Synthesis of covariant organopolysiloxane compound R1>
A reactor was charged with 61.26 g of methylhydrogenpolysiloxane represented by the average composition formula MD 15 DH 3.0 M, 32.32 g of tristrimethylsiloxyvinylsilane, and 6.42 g of diglycerin monoallyl ether under nitrogen flow. The mixture was heated to 65 ° C. with stirring. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 16 DR1 2.4 DR2 0.6 M was obtained. In the formula, R 1 and R 2 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
（比較例２）
＜共変性オルガノポリシロキサン化合物Ｒ２の合成＞
反応器に平均組成式 ＭＤ２９ＤＨ ７．３Ｍで表されるメチルハイドロジェンポリシロキサン５８．５３ｇ、トリストリメチルシロキシビニルシラン７．３０ｇ、ヘキサデセン２７．７２ｇ、ジグリセリンモノアリルエーテル６．４６ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ２９ＤＲ１ １．０ＤＲ２ １．３ＤＲ３ ５．０Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Comparative Example 2)
<Synthesis of covariant organopolysiloxane compound R2>
The reactor was charged with 58.53 g of methylhydrogenpolysiloxane represented by the average composition formula MD 29 DH 7.3 M, 7.30 g of tristrimethylsiloxyvinylsilane, 27.72 g of hexadecene, and 6.46 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 29 DR1 1.0 DR2 1.3 DR3 5.0 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
＜共変性オルガノポリシロキサン化合物Ｒ２の合成＞
反応器に平均組成式 ＭＤ２９ＤＨ ７．３Ｍで表されるメチルハイドロジェンポリシロキサン５８．５３ｇ、トリストリメチルシロキシビニルシラン７．３０ｇ、ヘキサデセン２７．７２ｇ、ジグリセリンモノアリルエーテル６．４６ｇを仕込み、窒素流通下で攪拌しながら６５℃まで加温した。白金触媒を０．０２ｇ添加し、１０時間反応を行った。アルカリ分解ガス発生法（残存したＳｉ－Ｈ基をＫＯＨのエタノール／水溶液によって分解し、発生した水素ガスの体積から反応率を計算する）により反応が完結したことを確認した。その後ろ過処理を施すことによって、平均組成式ＭＤ２９ＤＲ１ １．０ＤＲ２ １．３ＤＲ３ ５．０Ｍで表されるシロキサンデンドロン構造を有するジグリセリン共変性オルガノポリシロキサンを得た。式中、Ｒ１、Ｒ２およびＲ３は実施例１と同様である。この生成物は、淡黄色の粘性透明液体であった。 (Comparative Example 2)
<Synthesis of covariant organopolysiloxane compound R2>
The reactor was charged with 58.53 g of methylhydrogenpolysiloxane represented by the average composition formula MD 29 DH 7.3 M, 7.30 g of tristrimethylsiloxyvinylsilane, 27.72 g of hexadecene, and 6.46 g of diglycerin monoallyl ether. , The temperature was increased to 65 ° C. with stirring under the flow of nitrogen. 0.02 g of a platinum catalyst was added, and the reaction was carried out for 10 hours. It was confirmed that the reaction was completed by the alkaline decomposition gas generation method (the remaining Si—H group was decomposed with ethanol / aqueous solution of KOH, and the reaction rate was calculated from the volume of the generated hydrogen gas). Then, by performing a filtration treatment, a diglycerin co-modified organopolysiloxane having a siloxane dendron structure represented by the average composition formula MD 29 DR1 1.0 DR2 1.3 DR3 5.0 M was obtained. In the formula, R 1 , R 2 and R 3 are the same as in Example 1. The product was a pale yellow viscous transparent liquid.
上記の実施例１～４により得た共変性オルガノポリシロキサン化合物Ｐ１～Ｐ４、比較例１～２により得た比較用の共変性オルガノポリシロキサン化合物Ｒ１およびＲ２の平均組成式、ＨＬＢおよび粘度を表１にまとめる。Ｒ１、Ｒ２およびＲ３は実施例１と同様である。
The average composition formula, HLB and viscosity of the covariant organopolysiloxane compounds P1 to P4 obtained in Examples 1 to 4 and the comparative covariant organopolysiloxane compounds R1 and R2 obtained in Comparative Examples 1 and 2 are shown. Summarize in 1. R 1 , R 2 and R 3 are the same as in Example 1.
［分散安定性の評価］
表２に示す組成で油剤(パルミチン酸エチルヘキシル)中に上記の各共変性オルガノポリシロキサン(表中、Ｐ１～Ｒ２と記載)を溶解または分散し、これに粉体（平均粒径10×90nmの酸化チタン（製品名ＳＴＲ－１００Ａ－ＬＰ、堺化学工業製）およびジルコニアビーズ（０．８ ｍｍ Φ）を添加し、ペイントシェーカー（ＰＡＩＮＴ ＳＨＡＫＥＲ 浅田鉄工株式会社製）にて１５時間混合することにより粉体分散物（スラリー）を調製し、以下の評価基準により評価を行った結果を表２に示す。
〇： スラリー粘度 ２５００ｍＰａ・ｓ未満
△： スラリー粘度 ２５００ｍＰａ・ｓ以上
×： 流動性があるスラリーの作製不可 [Evaluation of dispersion stability]
Each of the above co-modified organopolysiloxanes (denoted as P1 to R2 in the table) is dissolved or dispersed in an oil (ethylhexyl palmitate) having the composition shown in Table 2, and a powder (average particle size 10 × 90 nm) is dissolved therein. Titanium oxide (product name STR-100A-LP, manufactured by Sakai Chemical Industry Co., Ltd.) and zirconia beads (0.8 mm Φ) are added and mixed with a paint shaker (PAINT SHAKER Asada Iron Works Co., Ltd.) for 15 hours to obtain powder. Table 2 shows the results of preparing a body dispersion (slurry) and evaluating it according to the following evaluation criteria.
〇: Slurry viscosity less than 2500 mPa · s Δ: Slurry viscosity 2500 mPa · s or more ×: Slurry with fluidity cannot be produced
表２に示す組成で油剤(パルミチン酸エチルヘキシル)中に上記の各共変性オルガノポリシロキサン(表中、Ｐ１～Ｒ２と記載)を溶解または分散し、これに粉体（平均粒径10×90nmの酸化チタン（製品名ＳＴＲ－１００Ａ－ＬＰ、堺化学工業製）およびジルコニアビーズ（０．８ ｍｍ Φ）を添加し、ペイントシェーカー（ＰＡＩＮＴ ＳＨＡＫＥＲ 浅田鉄工株式会社製）にて１５時間混合することにより粉体分散物（スラリー）を調製し、以下の評価基準により評価を行った結果を表２に示す。
〇： スラリー粘度 ２５００ｍＰａ・ｓ未満
△： スラリー粘度 ２５００ｍＰａ・ｓ以上
×： 流動性があるスラリーの作製不可 [Evaluation of dispersion stability]
Each of the above co-modified organopolysiloxanes (denoted as P1 to R2 in the table) is dissolved or dispersed in an oil (ethylhexyl palmitate) having the composition shown in Table 2, and a powder (average particle size 10 × 90 nm) is dissolved therein. Titanium oxide (product name STR-100A-LP, manufactured by Sakai Chemical Industry Co., Ltd.) and zirconia beads (0.8 mm Φ) are added and mixed with a paint shaker (PAINT SHAKER Asada Iron Works Co., Ltd.) for 15 hours to obtain powder. Table 2 shows the results of preparing a body dispersion (slurry) and evaluating it according to the following evaluation criteria.
〇: Slurry viscosity less than 2500 mPa · s Δ: Slurry viscosity 2500 mPa · s or more ×: Slurry with fluidity cannot be produced
表１に示す通り、本発明に係る共変性オルガノポリシロキサンＰ１～Ｐ４では、代表的な脂肪酸エステル油であるパルミチン酸エチルヘキシルを用いて、低粘度のスラリーを形成できたが、比較化合物Ｒ１，Ｒ２ではスラリーを作製不可または高粘度のスラリーとなり、脂肪酸エステル油に対して十分な粉体分散性能が実現できなかった。
As shown in Table 1, in the co-modified organopolysiloxanes P1 to P4 according to the present invention, a low-viscosity slurry could be formed using ethylhexyl palmitate, which is a typical fatty acid ester oil. In this case, the slurry could not be produced or became a highly viscous slurry, and sufficient powder dispersion performance could not be realized for fatty acid ester oil.
本発明に係る共変性オルガノポリシロキサンＰ１～Ｐ３については、パルミチン酸エチルヘキシル１６質量部の代わりに、デカメチルシクロペンタシロキサン１６質量部を使用して、同様な方法でスラリーを試作した評価結果を表１に併せて示す。その際の評価基準は以下の通りである。
〇〇：スラリー粘度 １０００ｍＰａ・ｓ未満、経時での増粘なし。
〇△：スラリー粘度 １０００ｍＰａ・ｓ未満、経時で増粘。 For the co-modified organopolysiloxanes P1 to P3 according to the present invention, 16 parts by mass of decamethylcyclopentasiloxane was used instead of 16 parts by mass of ethylhexyl palmitate, and the evaluation results of trial production of a slurry by the same method are shown. It is shown together with 1. The evaluation criteria at that time are as follows.
〇 〇: Slurry viscosity less than 1000 mPa · s, no thickening over time.
〇 △: Slurry viscosity is less than 1000 mPa · s, and the viscosity increases over time.
〇〇：スラリー粘度 １０００ｍＰａ・ｓ未満、経時での増粘なし。
〇△：スラリー粘度 １０００ｍＰａ・ｓ未満、経時で増粘。 For the co-modified organopolysiloxanes P1 to P3 according to the present invention, 16 parts by mass of decamethylcyclopentasiloxane was used instead of 16 parts by mass of ethylhexyl palmitate, and the evaluation results of trial production of a slurry by the same method are shown. It is shown together with 1. The evaluation criteria at that time are as follows.
〇 〇: Slurry viscosity less than 1000 mPa · s, no thickening over time.
〇 △: Slurry viscosity is less than 1000 mPa · s, and the viscosity increases over time.
表２の通り、本発明に係る共変性オルガノポリシロキサン、特にＰ１およびＰ２はデカメチルシクロペンタシロキサンについても低粘度かつ経時安定性に優れるスラリーを形成でき、シリコーン系の油剤に対しても、非シリコーン系の油剤に対しても、粉体分散性能に優れ、これらの油剤を使用乃至併用した外用剤組成物、化粧料において、粉体の分散安定性を改善できることが期待される。
As shown in Table 2, the co-modified organopolysiloxanes according to the present invention, particularly P1 and P2, can form a slurry having low viscosity and excellent stability over time even for decamethylcyclopentasiloxane, and are not suitable for silicone-based oils. It is also expected to have excellent powder dispersion performance with respect to silicone-based oils, and to improve powder dispersion stability in external preparation compositions and cosmetics using or using these oils.
［処方例］
その他、本発明の共変性オルガノポリシロキサンを用いる化粧料について、日本国特許出願2020-160317において、［処方例１］W/Oクッションファンデーション、［処方例２］W/O日焼け止め剤、［その他の処方例］が開示されている。 [Prescription example]
In addition, regarding cosmetics using the co-modified organopolysiloxane of the present invention, in Japanese patent application 2020-160317, [Prescription Example 1] W / O Cushion Foundation, [Prescription Example 2] W / O Sunscreen, [Others] Prescription example] is disclosed.
その他、本発明の共変性オルガノポリシロキサンを用いる化粧料について、日本国特許出願2020-160317において、［処方例１］W/Oクッションファンデーション、［処方例２］W/O日焼け止め剤、［その他の処方例］が開示されている。 [Prescription example]
In addition, regarding cosmetics using the co-modified organopolysiloxane of the present invention, in Japanese patent application 2020-160317, [Prescription Example 1] W / O Cushion Foundation, [Prescription Example 2] W / O Sunscreen, [Others] Prescription example] is disclosed.
Claims (11)
- ＨＬＢ＝（親水基部分の総分子量／総分子量）×２０
により定義されるＨＬＢの値が、０．５～２．０の範囲であり、下記構造式（１）で表される、２５℃における粘度が２００～１５００ｍPa・ｓの範囲である、共変性オルガノポリシロキサン。
構造式（１）：
Ｒ１は置換もしくは非置換の炭素原子数１～３０の一価炭化水素基または水素原子である。
Ｒ２は、炭素原子数６～３０の、置換もしくは非置換の、直鎖状もしくは分岐状の一価炭化水素基を表し、
Ｌ１はｉ＝１のとき、下記一般式（２）：
（式中、Ｒ１は前記同様の基であり、ＲＣは炭素原子数１～６のアルキル基またはフェニル基であり、Ｚは二価の有機基である。ｉはＬｉで示されるシリルアルキル基の階層を示し、該シリルアルキル基の繰り返し数である階層数がｃのとき１～ｃの整数であり、階層数ｃは１～１０の整数であり、Ｌｉ＋１はｉがｃ未満のときは該シリルアルキル基であり、ｉ＝ｃのときはメチル基またはフェニル基である。ａｉは０～３の範囲の数である）で示されるシロキサンデンドロン構造を有するシリルアルキル基、
下記一般式（２´）：
（式中、Ｒ１１はそれぞれ独立して置換若しくは非置換の炭素原子数１～３０の一価炭化水素基、水酸基又は水素原子であり、Ｒ１１のうち少なくとも一つは前記一価炭化水素基である。ｔは２～１０の範囲の数であり、ｒは１～５００の範囲の数である）で示される鎖状のオルガノシロキサン基、および
下記一般式（２´´）：
（式中、Ｒ１１及びｒは上記のとおりである）で示される鎖状のオルガノシロキサン基から選ばれる１種以上の基であり、
Ｑは二価の連結基（Ｚ）を介してケイ素原子に結合した、下記構造式（３―１）～（３－２）：
（式中、Ｚは炭素原子数２～２２のアルキレン基または－Ｒ６－Ｃ（＝Ｏ）－Ｏ－Ｒ７－で示される２価の有機基（Ｒ６は炭素原子数２～２２のアルキレン基であり、Ｒ７はエチレン基、プロピレン基、メチルエチレン基又はヘキシレン基から選択される基）を表し、ｍは１又は２である）
（式中、Ｚは上記のとおりであり、ｍ’は０又は１である）
で表される糖アルコールを含有してなる親水性基、および、下記構造式（３－３）～（３－５）：
（式中、Ｗは水素原子または炭素原子数１～２０のアルキル基。）
で表される親水性単位から選択される少なくとも１種以上の親水性単位を含有してなる親水性基であり、
（ｎ１＋ｎ２＋ｎ３＋ｎ４）は２～５０の範囲の数であり、ｎ１は０～２０、ｎ２は１～１０、ｎ３は０．１～１０、ｎ４は０．３～２．５の範囲の数である。｝ HLB = (total molecular weight of hydrophilic group part / total molecular weight) × 20
The HLB value defined by the above is in the range of 0.5 to 2.0, and the viscosity at 25 ° C. is in the range of 200 to 1500 mPa · s, which is represented by the following structural formula (1). Polysiloxane.
Structural formula (1):
R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom.
R 2 represents a substituted or unsubstituted linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms.
When L 1 is i = 1, the following general formula (2):
(In the formula, R 1 is the same group as described above, RC is an alkyl group or a phenyl group having 1 to 6 carbon atoms, Z is a divalent organic group, and i is a silyl represented by Li. It indicates the layer of the alkyl group, and when the number of layers which is the number of repetitions of the silylalkyl group is c, it is an integer of 1 to c, the number of layers c is an integer of 1 to 10, and Li + 1 is i less than c. When it is the silylalkyl group, when i = c, it is a methyl group or a phenyl group. Ai is a number in the range of 0 to 3), and a silylalkyl group having a siloxane dendron structure,
The following general formula (2'):
(In the formula, R 11 is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group. T is a number in the range of 2 to 10, r is a number in the range of 1 to 500), and the chain organosiloxane group represented by the following general formula (2 ′ ′) :.
(In the formula, R 11 and r are as described above), which is one or more groups selected from the chain-like organosiloxane groups.
Q is bonded to a silicon atom via a divalent linking group (Z), and has the following structural formulas (3-1) to (3-2):
(In the formula, Z is an alkylene group having 2 to 22 carbon atoms or a divalent organic group represented by -R 6 -C (= O) -OR 7- (R 6 is a divalent organic group having 2 to 22 carbon atoms. It is an alkylene group, where R7 represents a group selected from an ethylene group, a propylene group, a methylethylene group or a hexylene group), and m is 1 or 2).
(In the formula, Z is as described above and m'is 0 or 1).
A hydrophilic group containing a sugar alcohol represented by the following, and the following structural formulas (3-3) to (3-5):
(In the formula, W is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
A hydrophilic group containing at least one hydrophilic unit selected from the hydrophilic units represented by.
(N1 + n2 + n3 + n4) is a number in the range of 2 to 50, n1 is a number in the range of 0 to 20, n2 is a number in the range of 1 to 10, n3 is a number in the range of 0.1 to 10, and n4 is a number in the range of 0.3 to 2.5. } - 式（１）において、Ｌ１が下記一般式（２－１）または一般式（２－２）で表される官能基である、請求項１に記載の共変性オルガノポリシロキサン。
一般式（２－１）：
一般式（２－２）：
（式中、Ｒ１，ＲＣおよびＺは前記同様の基であり、ａ１およびａ２は各々独立に０～３の範囲の数である。） The covariant organopolysiloxane according to claim 1, wherein in the formula (1), L 1 is a functional group represented by the following general formula (2-1) or the general formula (2-2).
General formula (2-1):
General formula (2-2):
(In the equation, R 1 , RC and Z are the same groups as described above, and a 1 and a 2 are independently numbers in the range of 0 to 3). - 上記一般式（１）において、Ｑが、二価以上の連結基（オキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を有するものを除く）を介してケイ素原子に結合した、前記の構造式（４―１）～（４－３）で表されるグリセリン単位から選択される少なくとも１種以上のグリセリン単位を、その繰り返し数が平均して１．５～２．４の範囲で含有してなるジグリセリン誘導体基含有有機基（オキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を有するものを除く）である、請求項１または請求項２に記載の共変性オルガノポリシロキサン。 In the above general formula (1), Q is bonded to a silicon atom via a divalent or higher-valent linking group (excluding those having an oxyalkylene structure having an average value of the number of repetitions of an oxyalkylene unit of 2 or more). At least one type of glycerin unit selected from the glycerin units represented by the structural formulas (4-1) to (4-3) in the above, and the number of repetitions thereof is in the range of 1.5 to 2.4 on average. The co-modified organodase according to claim 1 or 2, which is a contained organic group containing a diglycerin derivative group (excluding those having an oxyalkylene structure having an average value of the number of repetitions of the oxyalkylene unit of 2 or more). Polysiloxane.
- 上記一般式（１）において、Ｑが、下記一般式（５－１）
（式中、Ｒ５は二価有機基（オキシアルキレン単位の繰り返し数の平均値が２以上のオキシアルキレン構造を有するものを除く）を表す）、又は、下記一般式（５－２）
（式中、Ｒ５は上記のとおりである）で表わされるジグリセリン誘導体基含有有機基であることを特徴とする、請求項１～請求項３のいずれか１項に記載の共変性オルガノポリシロキサン。 In the above general formula (1), Q is the following general formula (5-1).
(In the formula, R 5 represents a divalent organic group (excluding those having an oxyalkylene structure having an average value of the number of repetitions of the oxyalkylene unit of 2 or more)) or the following general formula (5-2).
The covariant organopoly according to any one of claims 1 to 3 , wherein R5 is an organic group containing a diglycerin derivative group represented by (in the formula, R5 is as described above). Siloxane. - ＨＬＢの値が、１．５～２．０の範囲であり、一般式（１）においてＲ２が炭素原子数８～２０のアルキル基であり、２５℃における粘度が７００～１４５０ｍPa・ｓの範囲である、請求項１～請求項４のいずれか１項に記載の共変性オルガノポリシロキサン。 The HLB value is in the range of 1.5 to 2.0, R2 is an alkyl group having 8 to 20 carbon atoms in the general formula (1), and the viscosity at 25 ° C. is in the range of 700 to 1450 mPa · s. The co-modified organopolysiloxane according to any one of claims 1 to 4.
- 請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサンを含有する粉体処理剤。 A powder treatment agent containing the covariant organopolysiloxane according to any one of claims 1 to 5.
- 請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサンを含有する界面活性剤または表面処理剤。 The surfactant or surface treatment agent containing the covariant organopolysiloxane according to any one of claims 1 to 5.
- （Ａ）請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサン
および （Ｂ）粉体又は着色剤を含有してなる粉体組成物。 (A) A powder composition containing the covariant organopolysiloxane according to any one of claims 1 to 5 and (B) a powder or a colorant. - （Ａ）請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサン、（Ｂ）粉体又は着色剤、および（Ｃ）５～１００℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される１以上の油剤を含有してなる油中粉体分散物。 (A) The co-modified organopolysiloxane according to any one of claims 1 to 5, (B) a powder or colorant, and (C) a silicone oil liquid at 5 to 100 ° C., non-polar. A powder dispersion in an oil containing one or more oils selected from an organic compound or a low-polarity organic compound.
- 請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサンを含有する外用剤組成物。 An external preparation composition containing the covariant organopolysiloxane according to any one of claims 1 to 5.
- （Ａ）請求項１～請求項５のいずれか１項に記載の共変性オルガノポリシロキサン、（Ｂ）粉体又は着色剤、および（Ｃ）５～１００℃で液状であるシリコーンオイル、非極性有機化合物または低極性有機化合物から選択される１以上の油剤を含有する、請求項１０に記載の外用剤組成物。 (A) The co-modified organopolysiloxane according to any one of claims 1 to 5, (B) a powder or colorant, and (C) a silicone oil liquid at 5 to 100 ° C., non-polar. The external preparation composition according to claim 10, which contains one or more oil agents selected from organic compounds or low-polarity organic compounds.
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| CN202180062975.5A CN116096787A (en) | 2020-09-25 | 2021-10-06 | Co-modified organopolysiloxane and use thereof |
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| KR20240066129A (en) | 2024-05-14 |
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